Processes for producing epsilon caprolactones and/or hydrates and/or esters thereof

ABSTRACT

This invention relates in part to processes for producing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof which comprise subjecting one or more substituted or unsubstituted penten-1-ols to carbonylation in the presence of a carbonylation catalyst, e.g., a metal-organophosphorus ligand complex catalyst, to produce said one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof. The substituted and unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof produced by the processes of this invention can undergo further reaction(s) to afford desired derivatives thereof, e.g., epsilon caprolactam. This invention also relates in part to reaction mixtures containing one or more substituted or unsubstituted epsilon caprolactones and/or hydrates and/or esters thereof as principal product(s) of reaction.

BRIEF SUMMARY OF THE INVENTION TECHNICAL FIELD

[0001] This invention relates in part to processes for selectivelyproducing one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof or reaction mixtures containingone or more substituted or unsubstituted epsilon caprolactones and/orhydrates and/or esters thereof. This invention also relates in part toreaction mixtures containing one or more substituted or unsubstitutedepsilon caprolactones and/or hydrates and/or esters thereof as thedesired product(s) of reaction.

BACKGROUND OF THE INVENTION

[0002] Epsilon caprolactone and/or certain hydrates and/or certainesters thereof are valuable intermediates which are useful, for example,in the production of epsilon caprolactam and polyesters. The processescurrently used to produce epsilon caprolactone and/or hydrates and/oresters thereof have various disadvantages. For example, the startingmaterials used to produce epsilon caprolactone and/or hydrates and/oresters thereof are relatively expensive. Accordingly, it would bedesirable to produce epsilon caprolactone and/or hydrates and/or estersthereof from relatively inexpensive starting materials and by a processwhich does not have the disadvantages of prior art processes.

DISCLOSURE OF THE INVENTION

[0003] It has been discovered that alcohols possessing internal olefinicunsaturation can be converted to epsilon caprolactones and/or hydratesand/or esters thereof. In particular, it has been surprisinglydiscovered that penten-1-ols, e.g., 3-penten-1-ols, can be converted toepsilon caprolactones, e.g., epsilon caprolactone, and/or hydratesand/or esters thereof by employing catalysts havingcarbonylation/isomerization capabilities.

[0004] This invention relates to processes for producing one or moresubstituted or unsubstituted epsilon caprolactones, e.g., epsiloncaprolactone, and/or hydrates and/or esters thereof which comprisesubjecting one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce said one ormore substituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof.

[0005] This invention also relates to processes for producing one ormore substituted or unsubstituted epsilon caprolactones, e.g., epsiloncaprolactone, and/or hydrates and/or esters thereof which comprise: (a)subjecting one or more substituted or unsubstituted alkadienes, e.g.,butadiene, to hydrocarbonylation in the presence of a hydrocarbonylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce one or more substituted or unsubstituted penten-1-ols; and (b)subjecting said one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce said one ormore substituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. The hydrocarbonylation reaction conditions instep (a) and the carbonylation reaction conditions in step (b) may bethe same or different. The hydrocarbonylation catalyst in step (a) andthe carbonylation catalyst in step (b) may be the same or different.

[0006] This invention further relates in part to a process for producinga batchwise or continuously generated reaction mixture comprising:

[0007] (1) one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates thereof,e.g., 6-hydroxyhexanoic acid, and/or esters thereof, e.g.,6-hydroxyhexanoic acid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

[0008] (2) one or more substituted or unsubstituted penten-1-ols, e.g.,cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3-penten-1-ol and/or 4-penten-1-ol;

[0009] (3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

[0010] (4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

[0011] (5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal; and

[0012] (6) optionally one or more substituted or unsubstitutedvaleraldehydes;

[0013] wherein the weight ratio of component (1) to the sum ofcomponents (3), (4), (5) and (6) is greater than about 0.1, preferablygreater than about 0.25, more preferably greater than about 1.0; and theweight ratio of component (2) to the sum of components (1), (3), (4),(5), and (6) is about 0 to about 100, preferably about 0.001 to about50; which process comprises subjecting one or more substituted orunsubstituted penten-1-ols to carbonylation in the presence of acarbonylation catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, to produce said batchwise or continuously generated reactionmixture.

[0014] This invention yet further relates in part to a process forproducing a batchwise or continuously generated reaction mixturecomprising:

[0015] (1) one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates thereof,e.g., 6-hydroxyhexanoic acid, and/or esters thereof, e.g.,6-hydroxyhexanoic acid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

[0016] (2) optionally one or more substituted or unsubstitutedpenten-1-ols, e.g., cis-2-penten-1-ol, trans-2-penten-1-ol,cis-3-penten-1-ol, trans-3-penten-1-ol and/or 4-penten-1-ol;

[0017] (3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

[0018] (4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

[0019] (5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

[0020] (6) optionally one or more substituted or unsubstitutedpentan-1-ols;

[0021] (7) optionally one or more substituted or unsubstitutedvaleraldehydes;

[0022] (8) optionally one or more substituted or unsubstitutedpentenals, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal,trans-3-pentenal and/or 4-pentenal;

[0023] (9) optionally one or more substituted or unsubstituted1,6-hexanedials, e.g., adipaldehyde;

[0024] (10) optionally one or more substituted 1,5-pentanedials, e.g.,2-methylglutaraldehyde;

[0025] (11) optionally one or more substituted 1,4-butanedials, e.g.,2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and

[0026] (12) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

[0027] wherein the weight ratio of component (1) to the sum ofcomponents (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) isgreater than about 0.1, preferably greater than about 0.25, morepreferably greater than about 1.0; and the weight ratio of component(12) to the sum of components (1), (2), (3), (4), (5), (6), (7), (8),(9), (10) and (11) is about 0 to about 100, preferably about 0.001 toabout 50;

[0028] which process comprises: (a) subjecting one or more substitutedor unsubstituted butadienes, e.g., butadiene, to hydrocarbonylation inthe presence of a hydrocarbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce one or moresubstituted or unsubstituted penten-1-ols; and (b) subjecting said oneor more substituted or unsubstituted penten-1-ols to carbonylation inthe presence of a carbonylation catalyst, e.g., a metal-organophosphorusligand complex catalyst, to produce said batchwise or continuouslygenerated reaction mixture. The hydrocarbonylation reaction conditionsin step (a) and the carbonylation reaction conditions in step (b) may bethe same or different. The hydrocarbonylation catalyst in step (a) andthe carbonylation catalyst in step (b) may be the same or different.

[0029] This invention also relates to a process for producing a reactionmixture comprising one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates and/or estersthereof which process comprises subjecting one or more substituted orunsubstituted penten-1-ols to carbonylation in the presence of acarbonylation catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, to produce said reaction mixture comprising one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof.

[0030] This invention further relates to a process for producing areaction mixture comprising one or more substituted or unsubstitutedepsilon caprolactones, e.g., epsilon caprolactone, and/or hydratesand/or esters thereof which process comprises: (a) subjecting one ormore substituted or unsubstituted alkadienes, e.g., butadiene, tohydrocarbonylation in the presence of a hydrocarbonylation catalyst,e.g., a metal-organophosphorus ligand complex catalyst, to produce oneor more substituted or unsubstituted penten-1-ols; and (b) subjectingsaid one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst, e.g., ametal-organophosphorus ligand complex catalyst, to produce said reactionmixture comprising one or more substituted or unsubstituted epsiloncaprolactones and/or hydrates and/or esters thereof. Thehydrocarbonylation reaction conditions in step (a) and the carbonylationreaction conditions in step (b) may be the same or different. Thehydrocarbonylation catalyst in step (a) and, the carbonylation catalystin step (b) may be the same or different.

[0031] The processes of this invention can achieve high selectivities ofalkadienes and penten-1-ols to epsilon caprolactones and/or hydratesand/or esters thereof, i.e., selectivities of alkadienes to epsiloncaprolactones and/or hydrates and/or esters thereof of at least 10% byweight and up to 85% by weight or greater may be achieved by theprocesses of this invention.

[0032] This invention yet further relates in part to a batchwise orcontinuously generated reaction mixture comprising:

[0033] (1) one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates thereof,e.g., 6-hydroxyhexanoic acid, and/or esters thereof, e.g.,6-hydroxyhexanoic acid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

[0034] (2) one or more substituted or unsubstituted penten-1-ols, e.g.,cis-2-penten-1-ol, trans-2-penten-1-ol, cis-3-penten-1-ol,trans-3:penten-1-ol and/or 4-penten-1-ol;

[0035] (3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

[0036] (4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

[0037] (5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal; and

[0038] (6) optionally one or more substituted or unsubstitutedvaleraldehydes;

[0039] wherein the weight ratio of component (1) to the sum ofcomponents (3), (4), (5) and (6) is greater than about 0.1, preferablygreater than about 0.25, more preferably greater than about 1.0; and theweight ratio of component (2) to the sum of components (1), (3), (4),(5), and (6) is about 0 to about 100, preferably about 0.001 to about50.

[0040] This invention also relates in part to a batchwise orcontinuously generated reaction mixture comprising:

[0041] (1) one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates thereof,e.g., 6-hydroxyhexanoic acid, and/or esters thereof, e.g.,6-hydroxyhexanoic acid esters such as cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone);

[0042] (2) optionally one or more substituted or unsubstitutedpenten-1-ols, e.g., cis-2-penten-1-ol, trans-2-penten-1-ol,cis-3-penten-1-ol, trans-3-penten-1-ol and/or 4-penten-1-ol;

[0043] (3) optionally one or more substituted or unsubstituted6-hydroxyhexanals, e.g., 6-hydroxyhexanal;

[0044] (4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof, e.g.,2-methyl-5-hydroxypentanal;

[0045] (5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof, e.g.,2-ethyl-4-hydroxybutanal;

[0046] (6) optionally one or more substituted or unsubstitutedpentan-1-ols;

[0047] (7) optionally one or more substituted or unsubstitutedvaleraldehydes;

[0048] (8) optionally one or more substituted or unsubstitutedpentenals, e.g., cis-2-pentenal, trans-2-pentenal, cis-3-pentenal,trans-3-pentenal and/or 4-pentenal;

[0049] (9) optionally one or more substituted or unsubstituted1,6-hexanedials, e.g., adipaldehyde;

[0050] (10) optionally one or more substituted 1,5-pentanedials, e.g.,2-methylglutaraldehyde;

[0051] (11) optionally one or more substituted 1,4-butanedials, e.g.,2,3-dimethylsuccinaldehyde and 2-ethylsuccinaldehyde; and

[0052] (12) one or more substituted or unsubstituted butadienes, e.g.,butadiene;

[0053] wherein the weight ratio of component (1) to the sum ofcomponents (2), (3), (4), (5), (6), (7), (8), (9), (10) and (11) isgreater than about 0.1, preferably greater than about 0.25, morepreferably greater than about 1.0; and the weight ratio of component(12) to the sum of components (1), (2), (3), (4), (5), (6), (7), (8),(9), (10) and (11) is about 0 to about 100, preferably about 0.001 toabout 50.

[0054] This invention further relates in part to a reaction mixturecomprising one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates and/or estersthereof in which said reaction mixture is prepared by a process whichcomprises subjecting one or more substituted or unsubstitutedpenten-1-ols to carbonylation in the presence of a carbonylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce said reaction mixture comprising one or more substituted orunsubstituted epsilon caprolactones and/or hydrates and/or estersthereof.

[0055] This invention yet further relates in part to a reaction mixturecomprising one or more substituted or unsubstituted epsiloncaprolactones, e.g., epsilon caprolactone, and/or hydrates and/or estersthereof in which said reaction mixture is prepared by a process whichcomprises: (a) subjecting one or more substituted or unsubstitutedalkadienes, e.g., butadiene, to hydrocarbonylation in the presence of ahydrocarbonylation catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, to produce one or more substituted or unsubstitutedpenten-1-ols; and (b) subjecting said one or more substituted orunsubstituted penten-1-ols to carbonylation in the presence of acarbonylation catalyst, e.g., a metal-organophosphorus ligand complexcatalyst, to produce said reaction mixture comprising one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof. The hydrocarbonylation reaction conditions instep (a) and the carbonylation reaction conditions in step (b) may bethe same or different. The hydrocarbonylation catalyst in step (a) andthe carbonylation catalyst in step (b) may be the same or different.

[0056] The reaction mixtures of this invention are distinctive insofaras the processes for their preparation achieve the generation of highselectivities of epsilon caprolactones and/or hydrates and/or estersthereof in a manner which can be suitably employed in a commercialprocess for the manufacture of epsilon caprolactones and/or hydratesand/or esters thereof. In particular, the reaction mixtures of thisinvention are distinctive insofar as the processes for their preparationallow for the production of epsilon caprolactones and/or hydrates and/oresters thereof in relatively high yields without generating largeamounts of byproducts, e.g., methyl valerolactone.

DETAILED DESCRIPTION Hydrocarbonylation Step or Stage

[0057] The hydrocarbonylation stage or step involves converting one ormore substituted or unsubstituted alkadienes to one or more substitutedor unsubstituted unsaturated alcohols. The hydrocarbonylation stage orstep may be conducted in one or more steps or stages, preferably a onestep process. As used herein, the term “hydrocarbonylation” iscontemplated to include all permissible hydrocarbonylation processeswhich involve converting one or more substituted or unsubstitutedalkadienes to one or more substituted or unsubstituted unsaturatedalcohols. In general, the hydrocarbonylation step or stage comprisesreacting one or more substituted or unsubstituted alkadienes, e.g.,butadienes, with carbon monoxide and hydrogen in the presence of ametal-ligand complex catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, and a promoter and optionally free ligand to produceone or more substituted or unsubstituted unsaturated alcohols, e.g.,penten-1-ols. A preferred hydrocarbonylation process useful in thisinvention is disclosed in U.S. patent application Ser. No. (D-17761),filed on an even date herewith, the disclosure of which is incorporatedherein by reference.

[0058] The hydrocarbonylation stage or step involves the production ofunsaturated alcohols by reacting an alkadiene with carbon monoxide andhydrogen in the presence of a metal-ligand complex catalyst andoptionally free ligand in a liquid medium that also contains a promoter.The reaction may be carried out in a continuous single pass mode in acontinuous gas recycle manner or more preferably in a continuous liquidcatalyst recycle manner as described below. The hydrocarbonylationprocessing techniques employable herein may correspond to any knownprocessing techniques.

[0059] The hydrocarbonylation process mixtures employable hereinincludes any solution derived from any corresponding hydrocarbonylationprocess that may contain at least some amount of four different mainingredients or components, i.e., the unsaturated alcohol product, ametal-ligand complex catalyst, a promoter and optionally free ligand,said ingredients corresponding to those employed and/or produced by thehydrocarbonylation process from whence the hydrocarbonylation processmixture starting material may be derived. By “free ligand” is meantligand that is not complexed with (tied to or bound to) the metal, e.g.,rhodium atom, of the complex catalyst. It is to be understood that thehydrocarbonylation process mixture compositions employable herein canand normally will contain minor amounts of additional ingredients suchas those which have either been deliberately employed in thehydrocarbonylation process or formed in situ during said process.Examples of such ingredients that can also be present include unreactedalkadiene starting material, carbon monoxide and hydrogen gases, and insitu formed type products, such as saturated alcohols and/or unreactedisomerized olefins corresponding to the alkadiene starting materials,and high boiling liquid byproducts, as well as other inert co-solventtype materials or hydrocarbon additives, if employed.

[0060] The catalysts useful in the hydrocarbonylation stage or stepinclude metal-ligand complex catalysts. The permissible metals whichmake up the metal-ligand complexes include Group 8, 9 and 10 metalsselected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru),iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) andmixtures thereof, with the preferred metals being rhodium, cobalt,iridium and ruthenium, more preferably rhodium, cobalt and ruthenium,especially rhodium. The permissible ligands include, for example,organophosphorus, organoarsenic and organoantimony ligands, or mixturesthereof, preferably organophosphorus ligands. The permissibleorganophosphorus ligands which make up the metal-organophosphorus ligandcomplexes and free organophosphorus ligand include mono-, di-, tri- andhigher poly-(organophosphorus) compounds, preferably those of highbasicity and low steric bulk. Illustrative permissible organophosphorusligands include, for example, organophosphines, organophosphites,organophosphonites, organophosphinites, organophosphorusnitrogen-containing ligands, organophosphorus sulfur-containing ligands,organophosphorus silicon-containing ligands and the like. Otherpermissible ligands include, for example, heteroatom-containing ligandssuch as described in U.S. patent application Ser. No. (D-17646-1), filedMar. 10, 1997, the disclosure of which is incorporated herein byreference. Mixtures of such ligands may be employed if desired in themetal-ligand complex catalyst and/or free ligand and such mixtures maybe the same or different. It is to be noted that the successful practiceof this invention does not depend and is not predicated on the exactstructure of the metal-ligand complex species, which may be present intheir mononuclear, dinuclear and/or higher nuclearity forms. Indeed, theexact structure is not known. Although it is not intended herein to bebound to any theory or mechanistic discourse, it appears that thecatalytic species may in its simplest form consist essentially of themetal in complex combination with the ligand and carbon monoxide whenused.

[0061] The term “complex” as used herein and in the claims means acoordination compound formed by the union of one or more electronicallyrich molecules or atoms capable of independent existence with one ormore electronically poor molecules or atoms, each of which is alsocapable of independent existence. For example, the ligands employableherein, i.e., organophosphorus ligands, may possess one or morephosphorus donor atoms, each having one available or unshared pair ofelectrons which are each capable of forming a coordinate covalent bondindependently or possibly in concert (e.g., via chelation) with themetal. Carbon monoxide (which is also properly classified as a ligand)can also be present and complexed with the metal. The ultimatecomposition of the complex catalyst may also contain an additionalligand, e.g., hydrogen or an anion satisfying the coordination sites ornuclear charge of the metal. Illustrative additional ligands include,e.g., halogen (Cl, Br, I), alkyl, aryl, substituted aryl, acyl, CF₃,C₂F₅, CN, (R)₂PO and RP(O)(OH)O (wherein each R is the same or differentand is a substituted or unsubstituted hydrocarbon radical, e.g., thealkyl or aryl), acetate, acetylacetonate, SO₄, BF₄, PF₆, NO₂, NO₃, CH₃O,CH₂═CHCH₂, CH₃CH═CHCH₂, C₆H₅CN, CH₃CN, NO, NH₃, pyridine, (C₂H₅)₃N,mono-olefins, diolefins and triolefins, tetrahydrofuran, and the like.It is of course to be understood that the complex species are preferablyfree of any additional organic ligand or anion that might poison thecatalyst and have an undue adverse effect on catalyst performance. It ispreferred in the metal-ligand complex catalyzed hydrocarbonylationprocesses that the active catalysts be free of halogen and sulfurdirectly bonded to the metal, although such may not be absolutelynecessary. Preferred metal-ligand complex catalysts includerhodium-organophosphine ligand complex catalysts.

[0062] The number of available coordination sites on such metals is wellknown in the art. Thus the catalytic species may comprise a complexcatalyst mixture, in their monomeric, dimeric or higher nuclearityforms, which are preferably characterized by at least onephosphorus-containing molecule complexed per metal, e.g., rhodium. Asnoted above, it is considered that the catalytic species of thepreferred catalyst employed in the hydrocarbonylation stage or step maybe complexed with carbon monoxide and hydrogen in addition to theorganophosphorus ligands in view of the carbon monoxide and hydrogen gasemployed by the hydrocarbonylation stage or step.

[0063] Among the organophosphines that may serve as the ligand of themetal-organophosphine complex catalyst and/or free organophosphineligand of the hydrocarbonylation process mixture starting materials aremono-, di-, tri- and poly-(organophosphines) such astriorganophosphines, trialkylphosphines, alkyldiarylphosphines,dialkylarylphosphines, dicycloalkylarylphosphines,cycloalkyldiarylphosphines, triaralkylphosphines,tricycloalkylphosphines, and triarylphosphines, alkyl and/or aryldiphosphines and bisphosphine mono oxides, as well as ionictriorganophosphines containing at least one ionic moiety selected fromthe salts of sulfonic acid, of carboxylic acid, of phosphonic acid andof quaternary ammonium compounds, and the like. Of course any of thehydrocarbon radicals of such tertiary non-ionic and ionicorganophosphines may be substituted if desired, with any suitablesubstituent that does not unduly adversely affect the desired result ofthe hydrocarbonylation process. The organophosphine ligands employablein the hydrocarbonylation stage or step and/or methods for theirpreparation are known in the art.

[0064] Illustrative triorganophosphine ligands may be represented by theformula:

[0065] wherein each R¹ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical, e.g., an alkyl, cycloalkylor aryl radical. In a preferred embodiment, each R¹ is the same ordifferent and is selected from primary alkyl, secondary alkyl, tertiaryalkyl and aryl. Suitable hydrocarbon radicals may contain from 1 to 24carbon atoms or greater. Illustrative substituent groups that may bepresent on the hydrocarbon radicals include, e.g., substituted orunsubstituted alkyl radicals, substituted or unsubstituted alkoxyradicals, substituted or unsubstituted silyl radicals such as —Si(R²)₃;amino radicals such as —N(R²)₂; acyl radicals such as —C(O)R²; carboxyradicals such as —C(O)OR²; acyloxy radicals such as —OC(O)R²; amidoradicals such as —C(O)N(R²)₂ and —N(R²)C(O)R²; ionic radicals such as—SO₃M wherein M represents inorganic or organic cationic atoms orradicals; sulfonyl radicals such as —SO₂R²; ether radicals such as —OR²;sulfinyl radicals such as —SOR²; selenyl radicals such as —SeR²;sulfenyl radicals such as —SR² as well as halogen, nitro, cyano,trifluoromethyl and hydroxy radicals, and the like, wherein each R²individually represents the same or different substituted orunsubstituted monovalent hydrocarbon radical, with the proviso that inamino substituents such as —N(R²)₂, each R² taken together can alsorepresent a divalent bridging group that forms a heterocyclic radicalwith the nitrogen atom and in amido substituents such as C(O)N(R²)₂ and—N(R²)C(O)R² each —R² bonded to N can also be hydrogen. Illustrativealkyl radicals include, e.g., methyl, ethyl, propyl, butyl, octyl,cyclohexyl, isopropyl and the like. Illustrative aryl radicals include,e.g., phenyl, naphthyl, fluorophenyl, difluorophenyl, benzoyloxyphenyl,carboethoxyphenyl, acetylphenyl, ethoxyphenyl, phenoxyphenyl,hydroxyphenyl; carboxyphenyl, trifluoromethylphenyl, methoxyethylphenyl,acetamidophenyl, dimethylcarbamylphenyl, tolyl, xylyl,4-dimethylaminophenyl, 2,4,6-trimethoxyphenyl and the like.

[0066] Illustrative specific organophosphines include, e.g.,trimethylphosphine, triethylphosphine, tributylphosphine,trioctylphosphine, diethylbutylphosphine, diethyl-n-propylphosphine,diethylisopropylphosphine, diethylbenzylphosphine,diethylcyclopentylphosphine, diethylcyclohexylphosphine,triphenylphosphine, tris-p-tolylphosphine,tris-p-methoxyphenylphosphine, tris-dimethylaminophenylphosphine,propyldiphenylphosphine, t-butyldiphenylphosphine,n-butyldiphenylphosphine, n-hexyldiphenylphosphine,cyclohexyldiphenylphosphine, dicyclohexylphenylphosphine,tricyclohexylphosphine, tribenzylphosphine, DIOP, i.e.,(4R,5R)-(−)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneand/or(4S,5S)-(+)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butaneand/or(4S,5R)-(−)-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,substituted or unsubstituted bicyclic bisphosphines such as1,2-bis(1,4-cyclooctylenephosphino)ethane,1,3-bis(1,4-cyclooctylenephosphino)propane,1,3-bis(1,5-cyclooctylenephosphino)propane and1,2-bis(2,6-dimethyl-1,4-cyclooctylenephosphino)ethane, substituted orunsubstituted bis(2,2′-diphenylphosphinomethyl)biphenyl such asbis(2,2′-diphenylphosphinomethyl)biphenyl andbis{2,2′-di(4-fluorophenyl)phosphinomethyl}biphenyl, MeC(CH₂PPh₂)₃(triphos), NaO₃S(C₆H₄)CH₂C(CH₂PPh₂)₃ (sulphos),bis(diphenylphosphino)ferrocene, bis(diisopropylphosphino)ferrocene,bis(diphenylphosphino)ruthenocene, as well as the alkali and alkalineearth metal salts of sulfonated triphenylphosphines, e.g., of(tri-m-sulfophenyl)phosphine and of (m-sulfophenyl)diphenyl-phosphineand the like.

[0067] The preferred organophosphorus ligands which make up themetal-organophosphorus ligand complex catalysts and freeorganophosphorus ligands are high basicity ligands. In general, thebasicity of the organophosphorus ligands should be greater than or equalto the basicity of triphenylphosphine (pKb of 2.74), e.g., from about2.74 to about 15. Suitable organophosphorus ligands have a pKb of about3 or greater, preferably a pKb of about 3 to about 12, and morepreferably a pKb of about 5 to about 12. pKb values for illustrativeorganophosphorus ligands useful in this invention are given in the TableI below. In addition, the organophosphorus ligands useful in thisinvention have a steric bulk sufficient to promote thehydrocarbonylation reaction. The steric bulk of monodentateorganophosphorus ligands should be lower than or equal to a Tolman coneangle of 210°, preferably lower than or equal to the steric bulk oftricyclohexylphosphine (Tolman cone angle =170°).

[0068] Organophosphorus ligands having desired basicity and steric bulkinclude, for example, substituted or unsubstitutedtri-primary-alkylphosphines (e.g., trioctylphosphine,diethylbutylphosphine, diethylisobutylphosphine),di-primary-alkylarylphosphines (e.g.,-diethylphenylphosphine,diethyl-p-N,N-dimethylphenylphosphine),di-primary-alkyl-mono-secondary-alkylphosphines (e.g.,diethylisopropylphosphine, diethylcyclohexylphosphine),di-primary-alkyl-tert-alkylphosphines (e.g.,diethyl-tert-butylphosphine), mono-primary-alkyl-diarylphosphines (e.g.,diphenylmethylphosphine),mono-primary-alkyl-di-secondary-alkylphosphines (e.g.,dicyclohexylethylphosphine), triarylphosphines (e.g.,tri-para-N,N-dimethylaminophenylphosphine),tri-secondarylalkylphosphines (e.g., tricyclohexylphosphine),mono-primaryalkyl-mono-secondaryalkyl-mono-tertiary alkylphosphines(e.g., ethylisopropyltert-butylphosphine) and the like. The permissibleorganophosphorus ligands may be substituted with any suitablefunctionalities and may include the promoter as described hereinbelow.TABLE I Organophosphorus Ligand pKb Trimethylphosphine 8.7Triethylphosphine 8.7 Tri-n-propylphosphine 8.7 Tri-n-butylphosphine 8.4Tri-n-octylphosphine 8.4 Tri-tert-butylphosphine 11.4Diethyl-tert-butylphosphine 10.1 Tricyclohexylphosphine 10Diphenylmethylphosphine 4.5 Diethylphenylphosphine 6.4Diphenylcyclohexylphosphine 5 Diphenylethylphosphine 4.9Tri(p-methoxyphenyl)phosphine 4.6 Triphenylphosphine 2.74Tri(p-N,N-dimethylaminophenyl)phosphine 8.65Tri(p-methylphenyl)phosphine 3.84

[0069] More particularly, illustrative metal-organophosphine complexcatalysts and illustrative free organophosphine ligands include, forexample, those disclosed in U.S. Pat. Nos. 3,239,566, 3,527,809;4,148,830; 4,247,486; 4,283,562; 4,400,548; 4,482,749 and 4,861,918, thedisclosures of which are incorporated herein by reference.

[0070] Other illustrative permissible organophosphorus ligands which maymake up the metal-organophosphorus ligand complexes and freeorganophosphorus ligands include, for example, those disclosed in U.S.Pat. Nos. 4,567,306, 4,599,206, 4,668,651, 4,717,775, 3,415,906,4,567,306, 4,599,206, 4,748,261, 4,769,498, 4,717,775, 4,885,401,5,202,297, 5,235,113, 5,254,741, 5,264,616, 5,312,996, 5,364,950,5,391,801, U.S. patent application Ser. No. (D-17646), filed Nov. 26,1996, and U.S. patent application Ser. No. (D-17459-1), filed on an evendate herewith, the disclosures of which are incorporated herein byreference.

[0071] The metal-ligand complex catalysts employable in this inventionmay be formed by methods known in the art. The metal-ligand complexcatalysts may be in homogeneous or heterogeneous form. For instance,preformed metal hydrido-carbonyl-organophosphorus ligand catalysts maybe prepared and introduced into the reaction mixture of ahydrocarbonylation process. More preferably, the metal-ligand complexcatalysts can be derived from a metal catalyst precursor which may beintroduced into the reaction medium for in situ formation of the activecatalyst. For example, rhodium catalyst precursors such as rhodiumdicarbonyl acetylacetonate, Rh₂O₃, Rh₄(CO)₁₂, Rh₆(CO)₁₆, Rh(NO₃)₃ andthe like may be introduced into the reaction mixture along with theorganophosphorus ligand for the in situ formation of the activecatalyst. In a preferred embodiment of this invention, rhodiumdicarbonyl acetylacetonate is employed as a rhodium precursor andreacted in the presence of a promoter with the organophosphine ligand toform a catalytic rhodium-organophosphine ligand complex precursor whichis introduced into the reactor along with excess free organophosphineligand for the in situ formation of the active catalyst. In any event,it is sufficient for the purpose of this invention that carbon monoxide,hydrogen and organophosphorus compound are all ligands that are capableof being complexed with the metal and that an activemetal-organophosphorus ligand catalyst is present in the reactionmixture under the conditions used in the hydrocarbonylation process.

[0072] More particularly, a catalyst precursor composition can be formedconsisting essentially of a solubilized metal-ligand complex precursorcatalyst, a promoter and free ligand. Such precursor compositions may beprepared by forming a solution of a metal starting material, such as ametal oxide, hydride, carbonyl or salt, e.g. a nitrate, which may or maynot be in complex combination with an organophosphorus ligand as definedherein. Any suitable metal starting material may be employed, e.g.rhodium dicarbonyl acetylacetonate, Rh₂O₃, Rh₄(CO)₁₂, Rh₆(CO)₁₆,Rh(NO₃)₃, and organophosphorus ligand rhodium carbonyl hydrides.Carbonyl and organophosphorus ligands, if not already complexed with theinitial metal, may be complexed to the metal either prior to or in situduring the hydrocarbonylation process.

[0073] By way of illustration, the preferred catalyst precursorcomposition of this invention consists essentially of a solubilizedrhodium carbonyl organophosphine ligand complex precursor catalyst, apromoter and free organophosphine ligand prepared by forming a solutionof rhodium dicarbonyl acetylacetonate, a promoter and an organophosphineligand as defined herein. The organophosphine ligand readily replacesone of the carbonyl ligands of the rhodium acetylacetonate complexprecursor at room temperature as witnessed by the evolution of carbonmonoxide gas. This substitution reaction may be facilitated by heatingthe solution if desired. Any suitable organic solvent in which both therhodium dicarbonyl acetylacetonate complex precursor and rhodiumorganophosphine ligand complex precursor are soluble can be employed.The amounts of rhodium complex catalyst precursor, organic solvent andorganophosphine ligand, as well as their preferred embodiments presentin such catalyst precursor compositions may obviously correspond tothose amounts employable in the hydrocarbonylation stage or step.Experience has shown that the acetylacetonate ligand of the precursorcatalyst is replaced after the hydrocarbonylation process has begun witha different ligand, e.g., hydrogen, carbon monoxide or organophosphineligand, to form the active complex catalyst as explained above. In acontinuous process, the acetylacetone which is freed from the precursorcatalyst under hydrocarbonylation conditions is removed from thereaction medium with the product alcohol and thus is in no waydetrimental to the hydrocarbonylation process. The use of such preferredrhodium complex catalytic precursor compositions provides a simpleeconomical and efficient method for handling the rhodium precursor metaland hydrocarbonylation start-up.

[0074] Accordingly, the metal-ligand complex catalysts used in theprocess of this invention consists essentially of the metal complexedwith carbon monoxide and a ligand, said ligand being bonded (complexed)to the metal in a chelated and/or non-chelated fashion. Moreover, theterminology “consists essentially of”, as used herein, does not exclude,but rather includes, hydrogen complexed with the metal, in addition tocarbon monoxide and the ligand. Further, such terminology does notexclude the possibility of other organic ligands and/or anions thatmight also be complexed with the metal. Materials in amounts whichunduly adversely poison or unduly deactivate the catalyst are notdesirable and so the catalyst most desirably is free of contaminantssuch as metal-bound halogen (e.g., chlorine, and the like) although suchmay not be absolutely necessary. The hydrogen and/or carbonyl ligands ofan active metal-organophosphine ligand complex catalyst may be presentas a result of being ligands bound to a precursor catalyst and/or as aresult of in situ formation, e.g., due to the hydrogen and carbonmonoxide gases employed in hydrocarbonylation stage or step.

[0075] As noted the hydrocarbonylation process involves the use of ametal-ligand complex catalyst as described herein. Of course mixtures ofsuch catalysts can also be employed if desired. The amount ofmetal-ligand complex catalyst present in the reaction medium of a givenhydrocarbonylation process need only be that minimum amount necessary toprovide the given metal concentration desired to be employed and whichwill furnish the basis for at least the catalytic amount of metalnecessary to catalyze the particular hydrocarbonylation process involvedsuch as disclosed, for example, in the above-mentioned patents. Ingeneral, the catalyst concentration can range from several parts permillion to several percent by weight. Organophosphorus ligands can beemployed in the above-mentioned catalysts in a molar ratio of generallyfrom about 0.5:1 or less to about 1000:1 or greater. The catalystconcentration will be dependent on the hydrocarbonylation processconditions and solvent employed.

[0076] In general, the organophosphorus ligand concentration inhydrocarbonylation process mixtures may range from between about 0.005and 25 weight percent based on the total weight of the reaction mixture.Preferably the ligand concentration is between 0.01 and 15 weightpercent, and more preferably is between about 0.05 and 10 weight percenton that basis.

[0077] In general, the concentration of the metal in thehydrocarbonylation process mixtures may be as high as about 2000 partsper million by weight or greater based on the weight of the reactionmixture. Preferably the metal concentration is between about 50 and 1500parts per million by weight based on the weight of the reaction mixture,and more preferably is between about 70 and 1200 parts per million byweight based on the weight of the reaction mixture.

[0078] In addition to the metal-ligand complex catalyst, free ligand(i.e., ligand that is not complexed with the rhodium metal) may also bepresent in the hydrocarbonylation process medium. The free ligand maycorrespond to any of the above-defined ligands discussed above asemployable herein. It is preferred that the free ligand be the same asthe ligand of the metal-ligand complex catalyst employed. However, suchligands need not be the same in any given process. Thehydrocarbonylation process may involve up to 100 moles, or higher, offree ligand per mole of metal in the hydrocarbonylation process medium.Preferably the hydrocarbonylation process is carried out in the presenceof from about 1 to about 50 moles of coordinatable phosphorus, morepreferably from about 1 to about 20 moles of coordinatable phosphorus,and most preferably from about 1 to about 8 moles of coordinatablephosphorus, per mole of metal present in the reaction medium; saidamounts of coordinatable phosphorus being the sum of both the amount ofcoordinatable phosphorus that is bound (complexed) to the rhodium metalpresent and the amount of free (non-complexed) coordinatable phosphoruspresent. Of course, if desired, make-up or additional coordinatablephosphorus can be supplied to the reaction medium of thehydrocarbonylation process at any time and in any suitable manner, e.g.to maintain a predetermined level of free ligand in the reaction medium.

[0079] As indicated above, the hydrocarbonylation catalyst may be inheterogeneous form during the reaction and/or during the productseparation. Such catalysts are particularly advantageous in thehydrocarbonylation of alkadienes to produce high boiling or thermallysensitive alcohols, so that the catalyst may be separated from theproducts by filtration or decantation at low temperatures. For example,the rhodium catalyst may be attached to a support so that the catalystretains its solid form during both the hydrocarbonylation and separationstages, or is soluble in a liquid reaction medium at high temperaturesand then is precipitated on cooling.

[0080] As an illustration, the rhodium catalyst may be impregnated ontoany solid support, such as inorganic oxides, (e.g., alumina, silica,titania, or zirconia) carbon, or ion exchange resins. The catalyst maybe supported on, or intercalated inside the pores of, a zeolite orglass; the catalyst may also be dissolved in a liquid film coating thepores of said zeolite or glass. Such zeolite-supported catalysts areparticularly advantageous for producing one or more regioisomericalcohols in high selectivity, as determined by the pore size of thezeolite. The techniques for supporting catalysts on solids, such asincipient wetness, which will be known to those skilled in the art. Thesolid catalyst thus formed may still be complexed with one or more ofthe ligands defined above. Descriptions of such solid catalysts may befound in for example: J. Mol. Cat. 1991, 70, 363-368; Catal. Lett. 1991,8, 209-214; J. Organomet. Chem, 1991, 403, 221-227; Nature, 1989, 339,454-455; J. Catal. 1985, 96, 563-573; J. Mol. Cat. 1987, 39, 243-259.

[0081] The rhodium catalyst may be attached to a thin film or membranesupport, such as cellulose acetate or polyphenylenesulfone, as describedin for example J. Mol. Cat. 1990, 63, 213-221.

[0082] The rhodium catalyst may be attached to an insoluble polymericsupport through an organophosphorus-containing ligand, such as aphosphine or phosphite, incorporated into the polymer. Suchpolymer-supported ligands are well known, and include such commerciallyavailable species as the divinylbenzene/polystyrene-supportedtriphenylphosphine. The supported ligand is not limited by the choice ofpolymer or phosphorus-containing species incorporated into it.Descriptions of polymer-supported catalysts may be found in for example:J. Mol. Cat. 1993, 83, 17-35; Chemtech 1983, 46; J. Am. Chem. Soc. 1987,109, 7122-7127.

[0083] In the heterogeneous catalysts described above, the catalyst mayremain in its heterogeneous form during the entire hydrocarbonylationand catalyst separation process. In another embodiment of the invention,the catalyst may be supported on a polymer which, by the nature of itsmolecular weight, is soluble in the reaction medium at elevatedtemperatures, but precipitates upon cooling, thus facilitating catalystseparation from the reaction mixture. Such “soluble” polymer-supportedcatalysts are described in for example: Polymer, 1992, 33, 161; J. Org.Chem. 1989, 54, 2726-2730.

[0084] When the rhodium catalyst is in a heterogeneous or supportedform, the reaction may be carried out in the gas phase. More preferably,the reaction is carried out in the slurry phase due to the high boilingpoints of the products, and to avoid decomposition of the productalcohols. The catalyst may then be separated from the product mixture byfiltration or decantation.

[0085] The processes of this invention can be operated over a wide rangeof reaction rates (m/L/h=moles of product/liter of reactionsolution/hour). Typically, the reaction rates are at least 0.01 m/L/h orhigher, preferably at least 0.1 m/L/h or higher, and more preferably atleast 0.5 m/L/h or higher. Higher reaction rates are generally preferredfrom an economic standpoint, e.g., smaller reactor size, etc.

[0086] The substituted and unsubstituted alkadiene starting materialsuseful in the hydrocarbonylation stage or step include, but are notlimited to, conjugated aliphatic diolefins represented by the formula:

[0087] wherein R₁ and R₂ are the same or different and are hydrogen,halogen or a substituted or unsubstituted hydrocarbon radical. Thealkadienes can be linear or branched and can contain substituents (e.g.,alkyl groups, halogen atoms, amino groups or silyl groups). Illustrativeof suitable alkadiene starting materials are butadiene, isoprene,dimethyl butadiene, cyclopentadiene and chloroprene. Most preferably,the alkadiene starting material is butadiene itself (CH₂═CH-CH═CH₂). Forpurposes of this invention, the term “alkadiene” is contemplated toinclude all permissible substituted and unsubstituted conjugateddiolefins, including all permissible mixtures comprising one or moresubstituted and unsubstituted conjugated diolefins. Illustrative ofsuitable substituted and unsubstituted alkadienes (including derivativesof alkadienes) include those permissible substituted and unsubstitutedalkadienes described in Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, 1996, the pertinent portions of which areincorporated herein by reference.

[0088] The particular hydrocarbonylation reaction conditions are notnarrowly critical and can be any effective hydrocarbonylation proceduressufficient to produce one or more unsaturated alcohols. The exactreaction conditions will be governed by the best compromise betweenachieving high catalyst selectivity, activity, lifetime and ease ofoperability, as well as the intrinsic reactivity of the startingmaterials in question and the stability of the starting materials andthe desired reaction product to the reaction conditions. Thehydrocarbonylation process conditions may include any suitable typehydrocarbonylation conditions heretofore employed for producingalcohols. The total pressure employed in the hydrocarbonylation processmay range in general from about 1 to about 10,000 psia, preferably fromabout 20 to 3000 psia and more preferably from about 50 to about 2000psia. The total pressure of the hydrocarbonylation process will bedependent on the particular catalyst system employed.

[0089] More specifically, the carbon monoxide partial pressure of thehydrocarbonylation process in general may range from about 1 to about3000 psia, and preferably from about 3 to about 1500 psia, while thehydrogen partial pressure in general may range from about 1 to about3000 psia, and preferably from about 3 to about 1500 psia. In general,the molar ratio of carbon monoxide to gaseous hydrogen may range fromabout 100:1 or greater to about 1:100 or less, the preferred carbonmonoxide to gaseous hydrogen molar ratio being from about 1:10 to about10:1. The carbon monoxide and hydrogen partial pressures will bedependent in part on the particular catalyst system employed. It isunderstood that carbon monoxide and hydrogen can be employed separately,either alone or in mixture with each other, i.e., synthesis gas, or maybe produced in situ under reaction conditions and/or be derived from thepromoter or solvent (not necessarily involving free hydrogen or carbonmonoxide). In an embodiment, the hydrogen partial pressure and carbonmonoxide partial pressure are sufficient to prevent or minimizederivatization, e.g., hydrogenation of penten-1-ols or furtherhydrocarbonylation of penten-1-ols or hydrogenation of alkadienes.

[0090] Further, the hydrocarbonylation process may be conducted at areaction temperature from about 20° C. to about 200° C., preferably fromabout 50° C. to about 150° C., and more preferably from about 65° C. toabout 115° C. The temperature must be sufficient for reaction to occur(which may vary with catalyst system employed), but not so high thatligand or catalyst decomposition occurs. At high temperatures (which mayvary with catalyst system employed), conversion of penten-1-ols toundesired byproducts may occur.

[0091] Of course, it is to be also understood that thehydrocarbonylation process conditions employed will be governed by thetype of unsaturated alcohol product desired.

[0092] To enable maximum levels of 3-penten-1-ols and/or 4-penten-1-olsand minimize 2-penten-1-ols, it is desirable to maintain some alkadienepartial pressure or when the alkadiene conversion is complete, thecarbon monoxide and hydrogen partial pressures should be sufficient toprevent or minimize derivatization, e.g., hydrogenation of penten-1-olsor further hydrocarbonylation of penten-1-ols or hydrogenation ofalkadienes.

[0093] In a preferred embodiment, the alkadiene hydrocarbonylation isconducted at an alkadiene partial pressure and/or a carbon monoxide andhydrogen partial pressures sufficient to prevent or minimizederivatization, e.g., hydrogenation of penten-1-ols or furtherhydrocarbonylation of penten-1-ols or hydrogenation of alkadienes. In amore preferred embodiment, the alkadiene, e.g., butadiene,hydrocarbonylation is conducted at an alkadiene partial pressure ofgreater than 0 psi, preferably greater than 5 psi, and more preferablygreater than 9 psi; at a carbon monoxide partial pressure of greaterthan 0 psi, preferably greater than 25 psi, and more preferably greaterthan 40 psi; and at a hydrogen partial pressure of greater than 0 psi,preferably greater than 25 psi, and more preferably greater than 80 psi.

[0094] The hydrocarbonylation process is also conducted in the presenceof a promoter. As used herein, “promoter” means an organic or inorganiccompound with an ionizable hydrogen of pKa of from about 1 to about 35.Illustrative promoters include, for example, protic solvents, organicand inorganic acids, alcohols, water, phenols, thiols, thiophenols,nitroalkanes, ketones, nitrites, amines (e.g., pyrroles anddiphenylamine), amides (e.g., acetamide), mono-, di- andtrialkylammonium salts, and the like. Approximate pKa values forillustrative promoters useful in this invention are given in the TableII below. The promoter may be present in the hydrocarbonylation reactionmixture either alone or incorporated into the ligand structure, eitheras the metal-ligand complex catalyst or as free ligand, or into thealkadiene structure. The desired promoter will depend on the nature ofthe ligands and metal of the metal-ligand complex catalysts. In general,a catalyst with a more basic metal-bound acyl or other intermediate willrequire a lower concentration and/or a less acidic promoter.

[0095] Although it is not intended herein to be bound to any theory ormechanistic discourse, it appears that the promoter may function totransfer a hydrogen ion to or otherwise activate a catalyst-bound acylor other intermediate. Mixtures of promoters in any permissiblecombination may be useful in this invention. A preferred class ofpromoters includes those that undergo hydrogen bonding, e.g., NH, OH andSH-containing groups and Lewis acids, since this is believed tofacilitate hydrogen ion transfer to or activation of the metal-boundacyl or other intermediate. In general, the amount of promoter may rangefrom about 10 parts per million or so up to about 99 percent by weightor more based on the total weight of the hydrocarbonylation processmixture starting materials. TABLE II Promoter pKa ROR (R = alkyl) 15-19ROH (R = aryl)  8-11 RCONHR (R = hydrogen or alkyl, 15-19 e.g.,acetamide) R₃NH⁺, R₂NH₂ ⁺(R = alkyl) 10-11 RCH₂NO₂  8-11 RCOCH₂R (R =alkyl) 19-20 RSH (R = alkyl) 10-11 RSH (R = aryl)  8-11 CNCH₂CN 11Diarylamine 21-24 Pyrrole 20 Pyrrolidine 34

[0096] The concentration of the promoter employed will depend upon thedetails of the catalyst system employed. Without wishing to be bound bytheory, the promoter component must be sufficiently acidic and insufficient concentration to transfer a hydrogen ion to or otherwiseactivate the catalyst-bound acyl or other intermediate. It is believedthat a promoter component acidity or concentration which is insufficientto transfer a hydrogen ion to or otherwise activate the catalyst-boundacyl or other intermediate will result in the formation of pentenalproducts, rather than the preferred penten-1-ol products. The ability ofa promoter component to transfer a hydrogen ion to or otherwise activatethe catalyst-bound acyl or other intermediate may be governed by severalfactors, for example, the concentration of the promoter component, theintrinsic acidity of the promoter component (the pKa), the compositionof the reaction medium (e.g., the reaction solvent) and the temperature.Promoters are chosen on the basis of their ability to transfer ahydrogen ion to or otherwise activate such a catalyst-bound acyl orother intermediate under reaction conditions sufficient to result in theformation of alcohol products, but not so high as to result indetrimental side reactions of the catalyst, reactants or products. Incases where the promoter component acidity or concentration isinsufficient to do so, aldehyde products (e.g., pentenals) are initiallyformed which may or may not be subsequently converted to unsaturatedalcohols, e.g., penten-1-ols.

[0097] In general, a less basic metal-bound acyl will require a higherconcentration of the promoter component or a more acidic promotercomponent to protonate or otherwise activate it fully, such that theproducts are more desired penten-1-ols, rather than pentenals. This canbe achieved by appropriate choice of promoter component. For example, anenabling concentration of protonated or otherwise activatedcatalyst-bound acyl or other intermediate can be achieved though the useof a large concentration of a mildly acidic promoter component, orthrough the use of a smaller concentration of a more acidic component.The promoter component is selected based upon its ability to produce thedesired concentration of protonated or otherwise activatedcatalyst-bound acyl or other intermediate in the reaction medium underreaction conditions. In general, the intrinsic strength of an acidicmaterial is generally defined in aqueous solution as the pKa, and not inreaction media commonly employed in hydrocarbonylation. The choice ofthe promoter and its concentration is made based in part upon thetheoretical or equivalent pH that the promoter alone at suchconcentration gives in aqueous solution at 22° C. The desiredtheoretical or equivalent pH of promoter component solutions should begreater than 0, preferably from about 1-12, more preferably from about2-10 and most preferably from 4-8. The theoretical or equivalent pH canbe readily calculated from values of pKa's at the appropriate promotercomponent concentration by reference to standard tables such as thosefound in “Ionization Constants of Organic Acids in Aqueous Solution”(IUPAC Chemical Data Series—No. 23) by E. P Seijeant and Boyd Dempsey,Pergamon Press (1979) and “Dissociation Constants of Inorganic Acids andBases in Aqueous Solution” (IUPAC Chemical Data Series—No. 19, by D. D.Perrin, Pergamon Press.

[0098] Depending on the particular catalyst and reactants employed,suitable promoters preferably include solvents, for example, alcohols(e.g., the unsaturated alcohol products such as penten-1-ols), thiols,thiophenols, selenols, tellurals, alkenes, alkynes, aldehydes, higherboiling byproducts, ketones, esters, amides, primary and secondaryamines, alkylaromatics and the like. Any suitable promoter which doesnot unduly adversely interfere with the intended hydrocarbonylationprocess can be employed. Permissible protic solvents have a pKa of about1-35, preferably a pKa of about 3-30, and more preferably a pKa of about5-25. Mixtures of one or more different solvents may be employed ifdesired.

[0099] In general, with regard to the production of unsaturatedalcohols, it is preferred to employ unsaturated alcohol promoterscorresponding to the unsaturated alcohol products desired to be producedand/or higher boiling byproducts as the main protic solvents. Suchbyproducts can also be preformed if desired and used accordingly.Illustrative preferred protic solvents employable in the production ofunsaturated alcohols, e.g., penten-1-ols, include alcohols (e.g.,pentenols, octanols, hexanediols), amines, thiols, thiophenols, ketones(e.g. acetone and methylethyl ketone), hydroxyaldehydes (e.g.,6-hydroxyaldehyde), lactols (e.g., 2-methylvalerolactol), esters (e.g.ethyl acetate), hydrocarbons (e.g. diphenylmethane, triphenylmethane),nitrohydrocarbons (e.g. nitromethane), 1,4-butanediols and sulfolane.Suitable protic solvents are disclosed in U.S. Pat. No. 5,312,996.

[0100] As indicated above, the promoter may be incorporated into theligand structure, either as the metal-ligand complex catalyst or as freeligand. Suitable ligand promoters which may be useful in this inventioninclude, for example, tris(2-hydroxyethyl)phosphine,tris(3-hydroxypropyl)phosphine, tris(2-hydroxyphenylphosphine),tris(4-hydroxyphenylphosphine), tris(3-carboxypropyl)phosphine,tris(3-carboxamidopropyl)phosphine, diphenyl(2-hydroxyphenyl)phosphine,diethyl(2-anilinophenyl)phosphine, and tris(3-pyrroyl)phosphine. The useof ligand promoters may by particularly beneficial in those instanceswhen the unsaturated alcohol product is not effective as a promoter. Aswith the organophosphorus ligands which make up themetal-organophosphorus ligand complex catalysts and freeorganophosphorus ligands, the organophosphorus ligand promoterspreferably are high basicity ligands having a steric bulk lower than orequal to a Tolman cone angle of 210°, preferably lower than or equal tothe steric bulk of tricyclohexylphosphine (Tolman cone angle=170°).Indeed, the organophosphorus ligand promoters may be employed asorganophosphorus ligands which make up the metal-organophosphorus ligandcomplex catalysts and free organophosphorus ligands. Mixtures ofpromoters comprising one or more ligand promoters and mixturescomprising one or more ligand promoters and one or more other promoters,e.g., protic solvents, may be useful in this invention.

[0101] In an embodiment of the invention, the hydrocarbonylation processmixture may consist of one or more liquid phases, e.g. a polar and anonpolar phase. Such processes are often advantageous in, for example,separating products from catalyst and/or reactants by partitioning intoeither phase. In addition, product selectivities dependent upon solventproperties may be increased by carrying out the reaction in thatsolvent. An application of this technology is the aqueous-phasehydrocarbonylation of alkadienes employing sulfonated phosphine ligands,hydroxylated phosphine ligands and aminated phosphine ligands for therhodium catalyst. A process carried out in aqueous solvent isparticularly advantageous for the preparation of alcohols because theproducts may be separated from the catalyst by extraction into asolvent.

[0102] As described herein, the phosphorus-containing ligand for therhodium hydrocarbonylation catalyst may contain any of a number ofsubstituents, such as cationic or anionic substituents, which willrender the catalyst soluble in a polar phase, e.g. water. Optionally, aphase-transfer catalyst may be added to the reaction mixture tofacilitate transport of the catalyst, reactants, or products into thedesired solvent phase. The structure of the ligand or the phase-transfercatalyst is not critical and will depend on the choice of conditions,reaction solvent, and desired products.

[0103] When the catalyst is present in a multiphasic system, thecatalyst may be separated from the reactants and/or products byconventional methods such as extraction or decantation. The reactionmixture itself may consist of one or more phases; alternatively, themultiphasic system may be created at the end of the reaction by forexample addition of a second solvent to separate the products from thecatalyst. See, for example, U.S. Pat. No. 5,180,854, the disclosure ofwhich is incorporated herein by reference.

[0104] In an embodiment of the process of this invention, an olefin canbe hydrocarbonylated along with an alkadiene using the above-describedmetal-ligand complex catalysts. In such cases, an alcohol derivative ofthe olefin is also produced along with the unsaturated alcohols, e.g.,penten-1-ols.

[0105] Mixtures of different olefinic starting materials can beemployed, if desired, in the hydrocarbonylation processes. Morepreferably the hydrocarbonylation process is especially useful for theproduction of unsaturated alcohols, by hydroformylating alkadienes inthe presence of alpha olefins containing from 2 to 30, preferably 4 to20, carbon atoms, including isobutylene, and internal olefins containingfrom 4 to 20 carbon atoms as well as starting material mixtures of suchalpha olefins and internal olefins. Commercial alpha olefins containingfour or more carbon atoms may contain minor amounts of correspondinginternal olefins and/or their corresponding saturated hydrocarbon andthat such commercial olefins need not necessarily be purified from sameprior to being hydroformylated.

[0106] Illustrative of other olefinic starting materials includealpha-olefins, internal olefins, 1,3-dienes, 1,2-dienes, alkylalkenoates, alkenyl alkanoates, alkenyl alkyl ethers, alkenols,alkenals, and the like, e.g., ethylene, propylene, 1-butene, 1-pentene,1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,1-octadecene, 1-nonadecene, 1-eicosene, 2-butene, 2-methyl propene(isobutylene), 2-methylbutene, 2-pentene, 2-hexene, 3-hexane, 2-heptene,cyclohexene, propylene dimers, propylene trimers, propylene tetramers,piperylene, isoprene, 2-ethyl-1-hexene, 2-octene, styrene,3-phenyl-1-propene, 1,4-hexadiene, 1,7-octadiene, 3-cyclohexyl-1-butene,allyl alcohol, allyl butyrate, hex-1-en-4-ol, oct-1-en-4-ol, vinylacetate, allyl acetate,-3-butenyl acetate, vinyl propionate, allylpropionate, methyl methacrylate, vinyl ethyl ether, vinyl methyl ether,vinyl cyclohexene, allyl ethyl ether, methyl pentenoate,n-propyl-7-octenoate, pentenals, e.g., 2-pentenal, 3-pentenal and4-pentenal; penten-1-ols, e.g., 2-penten-1-ol, 3-penten-1-ol and4-penten-1-ol; 3-butenenitrile, 3-pentenenitrile, 5-hexenamide, 4-methylstyrene, 4-isopropyl styrene, 4-tert-butyl styrene, alpha-methylstyrene, 4-tert-butyl-alpha-methyl styrene, 1,3-diisopropenylbenzene,eugenol, iso-eugenol, safrole, iso-safrole, anethol, 4-allylanisole,indene, limonene, beta-pinene, dicyclopentadiene, cyclooctadiene,camphene, linalool, and the like. Other illustrative olefinic compoundsmay include, for example, p-isobutylstyrene,2-vinyl-6-methoxynaphthylene, 3-ethenylphenyl phenyl ketone,4-ethenylphenyl-2-thienylketone, 4-ethenyl-2-fluorobiphenyl,4-(1,3-dihydro-1-oxo-2H-isoindol-2-yl)styrene,2-ethenyl-5-benzoylthiophene, 3-ethenylphenyl phenyl ether,propenylbenzene, isobutyl-4-propenylbenzene, phenyl vinyl ether and thelike. Other olefinic compounds include substituted aryl ethylenes asdescribed in U.S. Pat. No. 4,329,507, the disclosure of which isincorporated herein by reference.

[0107] In those instances where the promoter is not the solvent, thehydrocarbonylation processes encompassed by this invention are conductedin the presence of an organic solvent for the metal-ligand complexcatalyst and free ligand. The solvent may also contain dissolved waterup to the saturation limit. Depending on the particular catalyst andreactants employed, suitable organic solvents include, for example,alcohols, alkanes, alkenes, alkynes, ethers, aldehydes, higher boilinghydrocarbonylation byproducts, ketones, esters, amides, tertiary amines,aromatics and the like. Any suitable solvent which does not undulyadversely interfere with the intended hydrocarbonylation reaction can beemployed. Mixtures of one or more different solvents may be employed ifdesired. Illustrative preferred solvents employable in the production ofalcohols include ketones (e.g. acetone and methylethyl ketone), esters(e.g. ethyl acetate), hydrocarbons (e.g. toluene), nitrohydrocarbons(e.g. nitrobenzene), ethers (e.g. tetrahydrofuran (THF) and sulfolane.Suitable solvents are disclosed in U.S. Pat. No. 5,312,996. The amountof solvent employed is not critical to the subject invention and needonly be that amount sufficient to solubilize the catalyst and freeligand of the hydrocarbonylation reaction mixture to be treated. Ingeneral, the amount of solvent may range from about 5 percent by weightup to about 99 percent by weight or more based on the total weight ofthe hydrocarbonylation reaction mixture starting material.

[0108] Illustrative substituted and unsubstituted unsaturated alcoholintermediates that can be prepared by the processes of this inventioninclude one or more of the following: alkenols such ascis-3-penten-1-ol, trans-3-penten-1-ol, 4-penten-1-ol, cis-2-penten-1-oland/or trans-2-penten-1-ol, including mixtures comprising one or more ofthe above unsaturated alcohols. Illustrative of suitable substituted andunsubstituted unsaturated alcohols (including derivatives of unsaturatedalcohols) include those permissible substituted and unsubstitutedunsaturated alcohols which are described in Kirk-Othmer, Encyclopedia ofChemical Technology, Fourth Edition, 1996, the pertinent portions ofwhich are incorporated herein by reference.

[0109] As indicated above, it is generally preferred to carry out thehydrocarbonylation stage or step in a continuous manner. In general,continuous hydrocarbonylation processes may involve: (a)hydrocarbonylating the alkadiene starting material(s) with carbonmonoxide and hydrogen in a liquid homogeneous reaction mixturecomprising a solvent, the metal-ligand complex catalyst, and freeligand; (b) maintaining reaction temperature and pressure conditionsfavorable to the hydrocarbonylation of the alkadiene startingmaterial(s); (c) supplying make-up quantities of the alkadiene startingmaterial(s), carbon monoxide and hydrogen to the reaction medium asthose reactants are used up; and (d) recovering the desired alcoholhydrocarbonylation product(s) in any manner desired. The continuousreaction can be carried out in a single pass mode, i.e., wherein avaporous mixture comprising unreacted alkadiene starting material(s) andvaporized alcohol product is removed from the liquid reaction mixturefrom whence the alcohol product is recovered and make-up alkadienestarting material(s), carbon monoxide and hydrogen are supplied to theliquid reaction medium for the next single pass through withoutrecycling the unreacted alkadiene starting material(s). However, it isgenerally desirable to employ a continuous reaction that involves eithera liquid and/or gas recycle procedure. Such types of recycle procedureare known in the art and may involve the liquid recycling of themetal-ligand complex catalyst solution separated from the desiredalcohol reaction product(s).

[0110] As indicated above, the hydrocarbonylation stage or step mayinvolve a liquid catalyst recycle procedure. Such liquid catalystrecycle procedures are known in the art. For instance, in such liquidcatalyst recycle procedures it is commonplace to continuously orintermittently remove a portion of the liquid reaction product medium,containing, e.g., the alcohol product, the solubilized metal-ligandcomplex catalyst, free ligand, and organic solvent, as well asbyproducts produced in situ by the hydrocarbonylation and unreactedalkadiene starting material, carbon monoxide and hydrogen (syn gas)dissolved in said medium, from the hydrocarbonylation reactor, to adistillation zone, e.g., a vaporizer/separator wherein the desiredalcohol product is distilled in one or more stages under normal, reducedor elevated pressure, as appropriate, and separated from the liquidmedium. The vaporized or distilled desired alcohol product so separatedmay then be condensed and recovered in any conventional manner asdiscussed above. The remaining non-volatilized liquid residue whichcontains metal-ligand complex catalyst, solvent, free ligand and usuallysome undistilled alcohol product is then recycled back, with or with outfurther treatment as desired, along with whatever by-product andnon-volatilized gaseous reactants that might still also be dissolved insaid recycled liquid residue, in any conventional manner desired, to thehydrocarbonylation reactor, such as disclosed e.g., in theabove-mentioned patents. Moreover the reactant gases so removed by suchdistillation from the vaporizer may also be recycled back to the reactorif desired.

[0111] Recovery and purification of unsaturated alcohols may be by anyappropriate means, and may include distillation, phase separation,extraction, precipitation, absorption, crystallization, membraneseparation, derivative formation and other suitable means. For example,a crude reaction product can be subjected to a distillation-separationat atmospheric or reduced pressure through a packed distillation column.Reactive distillation may be useful in conducting the hydrocarbonylationreaction.

[0112] As indicated above, at the conclusion of (or during) thehydrocarbonylation process, the desired unsaturated alcohols, e.g.,penten-1-ols, may be recovered from the reaction mixtures used in theprocess of this invention. For instance, in a continuous liquid catalystrecycle reaction the portion of the liquid reaction mixture (containingpenten-1-ol product, catalyst, etc.) removed from the reactor can bepassed to a vaporizer/separator wherein the desired alcohol product canbe separated via distillation, in one or more stages, under normal,reduced or elevated pressure, from the liquid reaction solution,condensed and collected in a product receiver, and further purified ifdesired. The remaining non-volatilized catalyst containing liquidreaction mixture may then be recycled back to the reactor as may, ifdesired, any other volatile materials, e.g., unreacted alkadiene,together with any hydrogen and carbon monoxide dissolved in the liquidreaction after separation thereof from the condensed penten-1-olproduct, e.g., by distillation in any conventional manner. It isgenerally desirable to employ an organophosphorus ligand whose molecularweight exceeds that of the higher boiling alcohol oligomer byproductcorresponding to the penten-1-ols being produced in thehydrocarbonylation process. Another suitable recovery technique issolvent extraction or crystallization. In general, it is preferred toseparate the desired unsaturated alcohols from the catalyst-containingreaction mixture under reduced pressure and at low temperatures so as toavoid possible degradation of the organophosphorus ligand and reactionproducts. When an alpha-mono-olefin reactant is also employed, thealcohol derivative thereof can also be separated by the above methods.

[0113] More particularly, distillation and separation of the desiredalcohol product from the metal-ligand complex catalyst containingproduct solution may take place at any suitable temperature desired. Ingeneral, it is recommended that such distillation take place atrelatively low temperatures, such as below 150° C., and more preferablyat a temperature in the range of from about 50° C. to about 130° C. Itis also generally recommended that such alcohol distillation take placeunder reduced pressure, e.g., a total gas pressure that is substantiallylower than the total gas pressure employed during hydrocarbonylationwhen low boiling alcohols (e.g., C₅ and C₆) are involved or under vacuumwhen high boiling alcohols (e.g. C₇ or greater) are involved. Forinstance, a common practice is to subject the liquid reaction productmedium removed from the hydrocarbonylation reactor to a pressurereduction so as to volatilize a substantial portion of the unreactedgases dissolved in the liquid medium which now contains a much lowersynthesis gas concentration than was present in the hydrocarbonylationprocess medium to the distillation zone, e.g. vaporizer/separator,wherein the desired alcohol product is distilled. In general,distillation pressures ranging from vacuum pressures on up to total gaspressure of about 50 psig should be sufficient for most purposes.

[0114] While not wishing to be bound to any particular reactionmechanism, it is believed that the overall hydrocarbonylation reactiongenerally proceeds in one step, i.e., the one or more substituted orunsubstituted alkadienes (e.g., butadiene) are converted to one or moresubstituted or unsubstituted unsaturated alcohols (e.g., a 3-pentenoland/or 4-pentenol) either directly or through one or more intermediates(e.g., a 3-pentenal and/or 4-pentenal). This invention is not intendedto be limited in any manner by any particular reaction mechanism, butrather encompasses all permissible reaction mechanisms involved inhydrocarbonylating one or more substituted or unsubstituted alkadieneswith carbon monoxide and hydrogen in the presence of a metal-ligandcomplex catalyst and a promoter and optionally free ligand to produceone or more substituted or unsubstituted unsaturated alcohols.

[0115] As indicated above, the substituted and unsubstitutedpenten-1-ols produced by the hydrocarbonylation step of this inventioncan be separated by conventional techniques such as distillation,extraction, precipitation, crystallization, membrane separation, phaseseparation or other suitable means. For example, a crude reactionproduct can be subjected to a distillation-separation at atmospheric orreduced pressure through a packed distillation column. Reactivedistillation may be useful in conducting the hydrocarbonylation reactionstep. The subsequent carbonylation of the penten-1-ols may be conductedwithout the need to separate the penten-1-ols from the other componentsof the crude reaction mixtures.

Carbonylation Step or Stage

[0116] The carbonylation step or stage of this invention involvesconverting one or more substituted or unsubstituted penten-1-ols to oneor more substituted or unsubstituted epsilon caprolactones and/orhydrates and/or esters thereof. As used herein, the term “carbonylation”is contemplated to include, but are not limited to, all permissiblecarbonylation processes, e.g., cyclocarbonylation, hydroxycarbonylationand alkoxycarbonylation, which involve converting one or moresubstituted or unsubstituted penten-1-ols to one or more substituted orunsubstituted epsilon caprolactones and/or hydrates and/or estersthereof. In general, the carbonylation step or stage comprises reactingone or more substituted or unsubstituted penten-1-ols with carbonmonoxide in the presence of a catalyst and optionally a promoter toproduce one or more substituted or unsubstituted epsilon caprolactones,e.g., cyclocarbonylation, and/or hydrates thereof, e.g.,hydroxycarbonylation, and/or esters thereof, e.g., alkoxycarbonylation.

[0117] The carbonylation processes of this invention may be conducted inone or more steps or stages, preferably a one step process. Thecarbonylation reactions may be conducted in any permissible sequence soas to produce one or more substituted or unsubstituted epsiloncaprolactones and/or hydrates and/or esters thereof.

[0118] While not wishing to be bound to any particular reactionmechanism, it is believed that the overall carbonylation reactiongenerally proceeds in one step, i.e., the one or more substituted orunsubstituted penten-1-ols are converted to one or more substituted orunsubstituted epsilon caprolactones and/or hydrates and/or estersthereof either directly or through one or more intermediates. Thisinvention is not intended to be limited in any manner by any particularreaction mechanism, but rather encompasses all permissible carbonylationreactions which involve converting one or more substituted orunsubstituted penten-1-ols to one or more substituted or unsubstitutedepsilon caprolactones and/or hydrates and/or esters thereof.

[0119] Suitable carbonylation reaction conditions and processingtechniques and suitable carbonylation catalysts include those describedbelow. The carbonylation step or stage employed in the processes of thisinvention may be carried out as described below.

[0120] Penten-1-ols useful in the carbonylation are known materials andcan be prepared as described above or by known methods. Reactionmixtures comprising penten-1-ols may be useful herein. The amounts ofpenten-1-ols employed in the carbonylation step is not narrowly criticaland can be any amounts sufficient to produce epsilon caprolactonesand/or hydrates and/or esters thereof, preferably in high selectivities.

[0121] The particular carbonylation reaction conditions are not narrowlycritical and can be any effective carbonylation conditions sufficient toproduce the epsilon caprolactones and/or hydrates and/or esters thereofThe reactors may be stirred tanks, tubular reactors and the like. Theexact reaction conditions will be governed by the best compromisebetween achieving high catalyst selectivity, activity, lifetime and easeof operability, as well as the intrinsic reactivity of the penten-1-olsin question and the stability of the penten-1-ols and the desiredreaction product to the reaction conditions. Illustrative of certainreaction conditions that may be employed in the carbonylation processesare described, for example, in U.S. Pat. No. 4,602,114, the disclosureof which is incorporated herein by reference. Products may be recoveredafter a particular reaction zone and purified if desired althoughpreferably they are introduced to the next reaction zone withoutpurification. Recovery and purification may be by any appropriate means,which will largely be determined by the particular penten-1-ol employed,and may include distillation, phase separation, extraction, absorption,crystallization, derivative formation and the like.

[0122] The catalysts useful in the carbonylation process include, forexample, Group 6, 7, 8, 9 and 10 metal or metal complexes (supported orunsupported) in which suitable metals are selected from chromium (Cr),molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), rhodium(Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni),palladium (Pd), platinum (Pt), osmium (Os) and mixtures thereof, withthe preferred metals being cobalt, rhodium, iridium, nickel andpalladium, more preferably cobalt, rhodium, iridium and palladium,especially palladium. Other catalysts useful in the carbonylationprocess include, for example, Group 6, 7, 8, 9 and 10 metal-ligandcomplex catalysts as described above. The carbonylation catalysts may bein homogeneous or heterogeneous form. Such catalysts may be prepared bymethods known in the art. This invention is not intended to be limitedin any manner by the permissible catalysts or mixtures thereof Mixturesof catalysts may be employed if desired. It is to be noted that thesuccessful practice of this invention does not depend and is notpredicated on the exact structure of the catalyst species, which may bepresent in their mononuclear, dinuclear and/or higher nuclearity forms.Indeed, the exact structure is not known.

[0123] The permissible metals which make up the metal-ligand complexcatalysts include Group 6, 7, 8, 9 and 10 metals selected from chromium(Cr), molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re),rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), iron (Fe),nickel (Ni), palladium (Pd), platinum (Pt), osmium (Os) and mixturesthereof, with the preferred metals being cobalt, rhodium, iridium,nickel and palladium, more preferably cobalt, rhodium, iridium andpalladium, especially palladium.

[0124] The permissible ligands include, for example, organophosphorus,organoarsenic and organoantimony ligands, or mixtures thereof,preferably organophosphorus ligands. The permissible organophosphorusligands which make up the metal-ligand complexes includeorganophosphines, e.g., mono-, di-, tri- and poly-(organophosphines),and organophosphites, e.g., mono-, di-, tri- andpoly-(organophosphites). Other permissible organophosphorus ligandsinclude, for example, organophosphonites, organophosphinites, aminophosphines and the like. Other permissible ligands which make up themetal-ligand complex catalyst include organonitrogen species, forexample, mono-, di-, tri-, and polyamines, mono-, di-, tri-, andpolyimines, mono-, di-, tri-, and polypyridines, andheteroatom-stabilized carbenes, e.g., mono-, di-, tri-, andpolycarbenes. Still other permissible ligands include, for example,heteroatom-containing ligands such as described in U.S. patentapplication Ser. No. (D-17646-1), filed Mar. 10, 1997, the disclosure ofwhich is incorporated herein by reference. Mixtures of such ligands maybe employed if desired in the metal-ligand complex and/or free ligandand such mixtures may be the same or different. This invention is notintended to be limited in any manner by the permissible ligands ormixtures thereof Illustrative of such organophosphorus ligands aredescribed above.

[0125] The catalysts useful in the carbonylation process may be promotedor activated, for example, by acids, halides, quaternary ammonium orphosphonium halide salts, water, alcohols, hydrogen, nitrogen-containingcompounds or mixtures thereof. Permissible acids include Bronsted acidsand Lewis acids and mixtures thereof. The preferred Bronsted acidsinclude acids with pKa<7, e.g. carboxylic acids, sulfonic acids, HCl andHI, and the preferred Lewis acids include metal halides, metal alkylsand metal aryls, e.g., SnCl₂, MgCl₂, BPh₃, AlCl₃, SnPh₂ and MgBu₂. Otherpermissible acids include hydrophosphoric acid, pyrophosphoric acid,phosphotungstic acid, molybdic acid, and mixtures thereof. Permissiblehalides include fluoride, chloride, bromide and iodide, e.g., methyliodide, ethyl iodide, tetrabutylphosphonium iodide andtetrabutylammonium iodide. Permissible nitrogen-containing compoundsinclude N-heterocyclic bases, for example, pyridine, alkylatedpyridines, quinolines, lutidines, picolines, isoquinolines, alkylatedquinolines and isoquinolines, acridines and N-methyl-2-pyrrolidinone orN,N-dimethylaniline, N,N-diethylaniline, N,N-diethyltoluidine,N,N-dibutyltoluidine and N,N-dimethylformamide. The promoter may bepresent in the carbonylation reaction mixture either alone orincorporated into the ligand structure, either as the metal-ligandcomplex catalyst or as free ligand. The catalyst promoter should besufficient to generate an active catalytic species and to promoteremoval of product from the metal. The mole ratio of promoter to metalmay range from about 0.1:20 or less to about 20:1 or greater.

[0126] More particularly, illustrative metal-organophosphine complexcatalysts and metal catalysts useful in the carbonylation processinclude, for example, those disclosed in U.S. Pat. Nos. 4,602,114,4,960,906, 5,218,144, 5,420,346, 4,310,686, 4,692,549, 4,404,394,4,670,582, 4,786,443, 5,401,857, 4,634,780; European patent applicationNos. 662 467 and 329 252; and World Patent Application No. 9619427, thedisclosures of which are incorporated herein by reference.

[0127] In a preferred embodiment, the carbonylation reaction involvesconverting penten-1-ol in the liquid phase in the presence of carbonmonoxide, cobalt and pyridine to a reaction mixture comprising epsiloncaprolactones.

[0128] In another preferred embodiment, the carbonylation reactioninvolves converting penten-1-ol in the liquid phase in the presence ofcarbon monoxide, palladium and a bidentate organic phosphorus, antimonyor arsenic ligand to a reaction mixture comprising epsiloncaprolactones. The bidentate ligand has as bridging group a bivalentorganic compound having at least 2 carbon atoms, preferably abis(h-cyclopentadienyl) coordination group, of a transition metal.Preferably, iron is used as a transition metal in the metallocenecompound (the bridging group being a ferrocene). Preferably, phosphorusligands are used because these ligands are more stable than the arsenicor antimony based ligands. Such carbonylation reactions are known in theart. See, for example, the above U.S. Pat. Nos. 4,602,114.

[0129] Examples of suitable bidentate phosphine ligands according to theinvention are 1,1′-bis (diphenylphosphino)ferrocene;1,1′-bis(diisopropylphosphino)ferrocene;1,1′-bis(diisobutylphosphino)ferrocene;1,1′-bis(dipropylphosphino)ferrocene;1,1′-bis(dicyclohexylphosphino)ferrocene;1,1′-bis(isopropylcyclohexylphosphino)ferrocene;1,1′-bis(ditert-butylphosphino)ferrocene;1-(diisopropylphosphino)-1′-(phenylisopropylphosphino)ferrocene;1,1′-bis(di-2-thiophenylphosphino)ferrocene;1-(diisopropylphosphino)-1′-(diphenylphosphino)ferrocene;1,1′-bis(isopropylphenylphosphino)ferrocene; and 1,1′-bis(di-2-thiophenylphosphino)ferrocene.

[0130] All solvents are in principle useful, but it is also possible touse an excess of one of the reactants or byproducts in such an amountthat a suitable liquid phase is formed. A possible suitable reactant isthe penten-1-ol and examples of byproducts are the high boilingbyproducts. Examples of inert solvents are sulfoxides and sulfones, suchas dimethyl sulfoxide and diisopropyl sulfone; aromatic solvents such asbenzene, toluene and xylene; esters such as methyl acetate, methylvalerate, pentenoate esters and butyrolactone; nitrites such asacetonitrile and benzonitrile; ketones such as acetone or methylisobutylketone; and ethers such as anisole, trioxanone, diphenyl ether anddiisopropyl ether; and mixtures of these solvents.

[0131] The palladium may be present in the reaction mixture as aheterogeneous palladium compound or as a homogeneous palladium compound.However, homogeneous systems are preferred. Since palladium in situforms a complex with the bidentate ligand, the choice of the initialpalladium compound is in general not critical. Examples of homogeneouspalladium compounds are palladium salts of, for example, nitric acid,sulfonic acid, alkane carboxylic acids with not more than 12 carbonatoms or hydrogen halogenides (F, Cl, Br, I), but metallic palladium mayalso be used. Examples of such palladium compounds are PdCl₂, PdBr₂,PdI₂, Na₂PdI₄, K₂PdI₄, PdCl₂ (benzonitrile)₂ and bis(allylpalladiumchloride). Another group of suitable halogen-free palladium compoundsare palladium complexes such as palladium acetylacetonate (Pd(acac)₂),Pd(II) acetate, Pd(NO₃)₂, and palladium₂ (benzylidene acetone)₃. Anexample of a suitable heterogeneous palladium compound is palladium onan ion exchanger, such as for instance an ion exchanger containingsulfonic acid groups.

[0132] The bidentate ligand:palladium molar ratio is generally betweenabout 1:1 and 10:1. When this ratio is lower, palladium can precipitate,whereas when this ratio is higher, the catalytic effect is weaker andbyproducts such as high molecular weight products can form. The optimumratio will depend on the choice of the specific organic groups boundedto the phosphorus, arsenic or antimony atoms.

[0133] The carbonylation step is generally carried out at a temperaturebetween about 20° C. and 200° C. Preferably, the temperature is higherthan about 50° C. and lower than about 160° C. The (initial) pressure ofcarbon monoxide and optionally hydrogen can generally be chosen from awide range, e.g., from about 1 to about 10,000 psia. Of course, it isunderstood that materials that generate carbon monoxide under reactionconditions may also be used, for example, formic acid, carbon dioxideand hydrogen. The total pressure employed in the carbonylation processmay range in general from about 20 to about 3000 psia, preferably fromabout 50 to 1500 psia.

[0134] When a complex of the ligand and palladium is separately preparedbefore being added to the carbonylation reaction, an improved activityof the catalyst and an improved selectivity to the desired epsiloncaprolactone may occur compared to the situation in which this complexmay be formed in situ. Such a complex of palladium and ligand,hereinafter called catalyst precursor, can be prepared by mixing apalladium compound as described above with the ligand. This mixing ispreferably performed in a solvent. Temperature and pressure are notcritical. The temperature can be, for example, between about 0° C. and100° C. The pressure can be, for example, atmospheric pressure. Themixing is preferably performed in the absence of air. Examples ofpossible solvents include organic solvents, for example, benzene,toluene, xylene, or aliphatic solvents, for example, hexane, methylpentenoate, methanol, acetone and ethanol. Preferably the catalystprecursor is isolated from the mixture by crystallization of thecatalyst precursor under, for example, atmospheric pressure. The solidcatalyst precursor can be separated from the solvent by, for example,filtration or evaporation of the solvent. The solid catalyst precursoris air stable and can be easily supplied to the carbonylation reactionby, for example, dissolving the catalyst precursor in one of thereactants or solvents and supplying the resulting mixture to thereaction.

[0135] The carbonylation step may optionally be carried out in thepresence of a monodentate phosphine. The monodentate phosphine:bidentateligand molar ratio may range between about 1:10 and about 10:1.

[0136] In a preferred embodiment, this invention involves thepreparation of epsilon caprolactones by carbonylation of penten-1-ol asdescribed above wherein the following steps are performed:

[0137] (a) carbon monoxide, a source of palladium and the bidentateligand and optionally a protonic acid and a solvent are continuouslybrought into a reactor in which the carbonylation takes place;

[0138] (b) continuously separating part of the reaction mixture from thereactor;

[0139] (c) separating from the separated reaction mixture unreactedcarbon monoxide and unreacted penten-1-ol and returning these reactantsto step (a), and isolating the epsilon caprolactone; and

[0140] (d) returning the remaining mixture of step (c), containingpalladium and the bidentate ligand and optionally the solvent and theprotonic acid, to step (a). Preferably a part of the remaining mixtureof step (c) is separated from the mixture and led to a drain (purge) inorder to prevent a build up of high boiling byproducts in thecirculating reaction mixture.

[0141] Step (a) can be performed in several ways, for example, in acontinuously stirred tank reactor or a bubble column in which theproduct is simultaneously stripped from the liquid phase.

[0142] Separating the carbon monoxide, penten-1-ol and the epsiloncaprolactone from the reaction mixture in step (c) can be performed invarious ways. Generally the carbon monoxide is separated first from thereaction mixture in, for example, a simple gas-liquid separation unit.The penten-1-ol and the epsilon caprolactone can be separated from thereaction mixture in one step followed by isolating the epsiloncaprolactone from penten-1-ol. Preferably the penten-1-ols are separatedfrom the reaction mixture in a separate step followed by the isolationof the epsilon caprolactone from the remaining reaction mixture.Separation of the various compounds can be performed in various ways,for example, by simple flash operation or by distillation. The choice asto which unit operation is the most suitable will depend on the physicalproperties of the compounds to be separated.

[0143] The ratio of the remaining mixture of step (c) which is returnedto step (a) and the part which is processed to a drain will depend onthe amount of contaminants (for example, high boiling byproducts)allowed in the recirculating reaction mixture. When a large part will besent to the drain, a low degree of contamination in the recirculatingreaction mixture will be the result and vice versa. The ratio of theremaining mixture of step (c) which is returned to step (a) and the partwhich is processed to a drain will depend on the amount of contaminationformed in the carbonylation step and the acceptable level ofcontamination in the circulating process stream.

[0144] The part which is sent to the drain will contain apart from theabove mentioned contaminants also the valuable palladium and ligand andoptionally acid and solvent (provided acid and solvent are used in thecarbonylation step). Preferably the palladium, bidentate ligand, acidand solvent will be isolated from this mixture in order toadvantageously reuse these compounds in the carbonylation step (step(a)). Examples of possible processes to separate these valuablecompounds from some of the byproducts is by distillation,crystallization and extraction.

[0145] The epsilon caprolactones and/or hydrates and/or esters thereofproduced by the carbonylation step of this invention can be separated byconventional techniques such as distillation, extraction, precipitation,crystallization, membrane separation, phase separation or other suitablemeans. For example, a crude reaction product can be subjected to adistillation-separation at atmospheric or reduced pressure through apacked distillation column. Reactive distillation may be useful inconducting the carbonylation reaction step.

[0146] In the event that linear hydrates and/or esters of epsiloncaprolactone, e.g., 6-hydroxyhexanoic acid and/or 6-hydroxyhexanoic acidesters, are formed, an optional cyclization process can be conductedwhich involves converting one or more substituted or unsubstituted6-hydroxyhexanoic acids or one or more substituted or unsubstituted6-hydroxyhexanoic acid esters to one or more substituted orunsubstituted epsilon caprolactones in one or more steps or stages. Asused herein, the term “cyclization” is contemplated to include allpermissible cyclization processes which involve converting one or moresubstituted or unsubstituted linear hydrates of epsilon caprolactone,e.g., 6-hydroxyhexanoic acids, or one or more substituted orunsubstituted linear esters of epsilon caprolactone, e.g.,6-hydroxyhexanoic acid esters, to one or more substituted orunsubstituted epsilon caprolactones. As used herein, the term “epsiloncaprolactone” is contemplated to include all permissible substituted orunsubstituted epsilon caprolactones which may be derived from one ormore substituted or unsubstituted linear hydrates of epsiloncaprolactone, e.g., 6-hydroxyhexanoic acids, or one or more substitutedor unsubstituted linear esters of epsilon caprolactone, e.g.,6-hydroxyhexanoic acid esters.

[0147] 6-Hydroxyhexanoic acids and 6-hydroxyhexanoic acid esters usefulin the cyclization step are known materials and can be prepared asdescribed above. Reaction mixtures comprising 6-hydroxyhexanoic acidsand/or 6-hydroxyhexanoic acid esters may be useful herein. The amountsof 6-hydroxyhexanoic acids and 6-hydroxyhexanoic acid esters employed inthe cyclization step is not narrowly critical and can be any amountssufficient to produce epsilon caprolactones, preferably in highselectivities.

[0148] The cyclization reaction can be conducted at a temperature offrom about 0° C. to about 400° C. for a period of about 1 hour or lessto about 4 hours or longer with the longer time being used at the lowertemperature, preferably from about 50° C. to about 350° C. for about 1hour or less to about 2 hours or longer, and more preferably at about50° C. to about 200° C. for about 1 hour or less.

[0149] The cyclization reaction can be conducted over a wide range ofpressures ranging from subatmospheric to about 3000 psig. It ispreferable to conduct the cyclization reaction at pressures of fromabout 50 psig to about 2500 psig. The cyclization reaction is preferablyeffected in the liquid or vapor states or mixtures thereof.

[0150] The amount of cyclization catalyst used is dependent on theparticular cyclization catalyst employed and can range from about 0.01weight percent or less to about 10 weight percent or greater of thetotal weight of the starting materials.

[0151] Such cyclization reactions may be performed in any appropriatesolvent, under any appropriate atmosphere, or in the gas phase. Suchsolvents and atmospheres are chosen to allow the most desirable catalystperformance. For example, reactions may be performed under hydrogen gasin order to stabilize the catalyst from decomposition reactions tounproductive catalysts. Suitable solvents include ethers, esters,lactones (such as epsilon caprolactone), ketones, aliphatic or aromatichydrocarbons, fluorocarbons, silicones, polyethers, chlorinatedhydrocarbons and the like. The cyclization may be carried out using thepure epsilon caprolactone precursor or the epsilon caprolactoneprecursor and a mixture of byproducts from the earlier stages of thereaction sequence. If the transformation is carried out in the presenceof water, it is desirable that the solvent mixture employed be capableof dissolving all components of the reaction mixture, except anyheterogeneous catalysts that may be employed.

[0152] The cyclization process may be carried out in one or more stepsor stages and in any permissible sequence of steps or stages. In a onestep process, epsilon caprolactone is the major product leaving thereaction zone.

[0153] The particular cyclization reaction conditions are not narrowlycritical and can be any effective cyclization conditions sufficient toproduce the epsilon caprolactone. The reactors may be stirred tanks,tubular reactors and the like. The exact reaction conditions will begoverned by the best compromise between achieving high catalystselectivity, activity, lifetime and ease of operability, as well as theintrinsic reactivity of the epsilon caprolactone precursor in questionand the stability of the epsilon caprolactone precursor and the desiredreaction product to the reaction conditions. Products may be recoveredafter a particular reaction zone and purified if desired althoughpreferably they are introduced to the next reaction zone withoutpurification. Recovery and purification may be by any appropriate means,which will largely be determined by the particular epsilon caprolactoneprecursor employed, and may include distillation, phase separation,extraction, absorption, crystallization, derivative formation and thelike.

[0154] The cyclization reaction of an epsilon caprolactone precursor mayor may not need a catalyst, depending on the particular epsiloncaprolactone precursor employed. Although it may not be absolutelynecessary to employ a catalyst, it still may be desirable to do so toimprove the selectivity or rate of the transformation. Other epsiloncaprolactone precursors may necessitate the use of an appropriatecatalyst. Since the mechanism of the cyclization reaction depends on theepsilon caprolactone precursor, the useful catalysts will be selectedbased upon the epsilon caprolactone precursor employed.

[0155] A two phase system may also be used, providing adequate mixing isachieved. Such a system, however, may be used to facilitate recovery ofepsilon caprolactone after the cyclization reaction by extraction, phaseseparation or crystallization.

[0156] The epsilon caprolactones produced by the cyclization step ofthis invention can be separated by conventional techniques such asdistillation, extraction, precipitation, crystallization, membraneseparation, phase separation or other suitable means. For example, acrude reaction product can be subjected to a distillation-separation atatmospheric or reduced pressure through a packed distillation column.Reactive distillation may be useful in conducting the cyclizationreaction step.

[0157] As indicated herein, the processes of this invention may produce,in addition to one or more substituted or unsubstituted epsiloncaprolactones, other desirable products, for example, hydrates ofepsilon caprolactones such as 6-hydroxyhexanoic acid, and esters such as6-hydroxyvaleric acid esters or esters thereof (e.g.,cis-3-pentenyl-6-hydroxyhexanoate, trans-3-pentenyl-6-hydroxyhexanoate,4-pentenyl-6-hydroxyhexanoate, poly(epsilon caprolactone)). Thisinvention is not intended to be limited in any manner by the permissibleproducts produced by the processes of this invention or the permissibleproducts contained in the reaction mixtures of this invention.

[0158] Illustrative epsilon caprolactones that can be prepared by theprocesses of this invention include epsilon caprolactone and substitutedepsilon caprolactones (e.g., alpha, beta, gamma and delta substitutedepsilon caprolactones). Illustrative of suitable substituted andunsubstituted epsilon caprolactones (including derivatives of epsiloncaprolactones) include those permissible substituted and unsubstitutedepsilon caprolactones which are described in Kirk-Othmer, Encyclopediaof Chemical Technology, Fourth Edition, 1996, the pertinent portions ofwhich are incorporated herein by reference.

[0159] Illustrative hydrates of epsilon caprolactones that can beprepared by the processes of this invention include substituted orunsubstituted 6-hydroxyhexanoic acids. Illustrative of suitablesubstituted and unsubstituted hydrates of epsilon caprolactones(including derivatives of epsilon caprolactones) include thosepermissible substituted and unsubstituted hydrates of epsiloncaprolactones which may be described in Kirk-Othmer, Encyclopedia ofChemical Technology, Fourth Edition, 1996, the pertinent portions ofwhich are incorporated herein by reference.

[0160] Illustrative esters that can be prepared by the processes of thisinvention include substituted or unsubstituted 6-hydroxyvaleric acidesters or esters thereof, e.g., cis-3-pentenyl-6-hydroxyhexanoate,trans-3-pentenyl-6-hydroxyhexanoate, 4-pentenyl-6-hydroxyhexanoate,poly(epsilon caprolactone). Illustrative of suitable substituted andunsubstituted esters (including derivatives of such esters) includethose permissible substituted and unsubstituted esters which aredescribed in Kirk-Othmer, Encyclopedia of Chemical Technology, FourthEdition, 1996, the pertinent portions of which are incorporated hereinby reference.

[0161] The epsilon caprolactone, 6-hydroxyhexanoic acid and6-hydroxyvaleric acid ester products have a wide range of utilities thatare well known in the art, e.g., they are useful as startingmaterials/intermediates in the production of epsilon caprolactam andpolyesters. The 6-hydroxyvaleric acid esters or esters thereof are alsouseful as solvents.

[0162] A process for producing epsilon caprolactones from one or moresubstituted or unsubstituted alkadienes is disclosed in copending U.S.patent application Ser. No. (D-17490), filed Apr. 24, 1996, thedisclosure of which is incorporated herein by reference. Another processinvolving the reductive hydroformylation of one or more substituted orunsubstituted alkadienes to produce one or more substituted orunsubstituted penten-1-ols and carbonylation of the penten-1-ols toproduce epsilon caprolactones is disclosed in copending U.S. patentapplication Ser. No. (D-17776), filed on an even date herewith, thedisclosure of which is incorporated herein by reference.

[0163] An embodiment of this invention relates to a process forproducing one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof which/comprises:

[0164] (a) subjecting one or more substituted or unsubstitutedalkadienes, e.g., butadiene, to hydrocarbonylation in the presence of ahydrocarbonylation catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, to produce one or more substituted or unsubstitutedunsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols;

[0165] (b) optionally separating the 3-penten-1-ols, 4-penten-1-oland/or 2-penten-1-ols from the hydrocarbonylation catalyst; and

[0166] (c) subjecting said one or more substituted or unsubstitutedunsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols to carbonylation in the presence of a carbonylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof. The reaction conditions in steps(a) and (c) may be the same or different and the hydrocarbonylation andcarbonylation catalysts in steps (a) and (c) may be the same ordifferent.

[0167] Yet another embodiment of this invention relates to a process forproducing one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof which comprises:

[0168] (a) subjecting one or more substituted or unsubstitutedalkadienes, e.g., butadiene, to hydrocarbonylation in the presence of ahydrocarbonylation catalyst, e.g., a metal-organophosphorus ligandcomplex catalyst, to produce one or more substituted or unsubstitutedunsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols;

[0169] (b) optionally separating the 3-penten-1-ols, 4-penten-1-oland/or 2-penten-1-ols from the hydrocarbonylation catalyst;

[0170] (c) optionally subjecting the 2-penten-1-ols and/or3-penten-1-ols to isomerization in the presence of a heterogeneous orhomogeneous olefin isomerization catalyst to partially or completelyisomerize the 2-penten-1-ols and/or 3-penten-1-ols to 3-penten-1-olsand/or 4-penten-1-ol; and

[0171] (d) subjecting said one or more substituted or unsubstitutedunsaturated alcohols comprising 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols to carbonylation in the presence of a carbonylationcatalyst, e.g., a metal-organophosphorus ligand complex catalyst, toproduce one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof. The reaction conditions in steps(a) and (d) may be the same or different and the hydrocarbonylation andcarbonylation catalysts in steps (a) and (d) may be the same ordifferent.

[0172] The olefin isomerization catalyst in step (c) may be any of avariety of homogeneous or heterogeneous transition metal-based catalysts(particularly Ni, Rh, Pd, Pt, Co, Ru, or Ir), or may be a heterogeneousor homogeneous acid catalyst (particularly any acidic zeolite, polymericresin, or source of H+, any of which may be modified with one or moretransition metals). Such olefin isomerization catalysts are known in theart and the isomerization can be conducted by conventional proceduresknown in the art. As used herein, the term “isomerization” iscontemplated to include, but are not limited to, all permissibleisomerization processes which involve converting one or more substitutedor unsubstituted 2-penten-1-ols and/or 3-penten-1-ols to one or moresubstituted or unsubstituted 4-penten-1-ols.

[0173] When the processes of this invention are conducted in two stages(i.e., first producing 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols under one set of conditions and then producing epsiloncaprolactone from the 3-penten-1-ols, 4-penten-1-ol and/or2-penten-1-ols under another set of conditions), it is preferred toconduct the first stage at a temperature from 75° C. to 110° C. and at atotal pressure from 250 psi to 1000 psi and to conduct the second stageat a temperature from 60° C. to 120° C. and at a pressure from 5 psi to500 psi. The same or different catalysts can be used in the first andsecond stages. The other conditions can be the same or different in bothstages.

[0174] The processes of this invention can be operated over a wide rangeof reaction rates (m/L/h=moles of product/liter of reactionsolution/hour). Typically, the reaction rates are at least 0.01 m/L/h orhigher, preferably at least 0.1 m/L/h or higher, and more preferably atleast 0.5 m/L/h or higher. Higher reaction rates are generally preferredfrom an economic standpoint, e.g., smaller reactor size, etc.

[0175] The processes of this invention may be carried out using, forexample, a fixed bed reactor, a fluid bed reactor, a continuous stirredtank reactor (CSTR) or a slurry reactor. The optimum size and shape ofthe catalysts will depend on the type of reactor used. In general, forfluid bed reactors, a small, spherical catalyst particle is preferredfor easy fluidization. With fixed bed reactors, larger catalystparticles are preferred so the back pressure within the reactor is keptreasonably low.

[0176] The processes of this invention can be conducted in a batch orcontinuous fashion, with recycle of unconsumed starting materials ifrequired. The reaction can be conducted in a single reaction zone or ina plurality of reaction zones, in series or in parallel or it may beconducted batchwise or continuously in an elongated tubular zone orseries of such zones. The materials of construction employed should beinert to the starting materials during the reaction and the fabricationof the equipment should be able to withstand the reaction temperaturesand pressures. Means to introduce and/or adjust the quantity of startingmaterials or ingredients introduced batchwise or continuously into thereaction zone during the course of the reaction can be convenientlyutilized in the processes especially to maintain the desired molar ratioof the starting materials. The reaction steps may be effected by theincremental addition of one of the starting materials to the other.Also, the reaction steps can be combined by the joint addition of thestarting materials. When complete conversion is not desired or notobtainable, the starting materials can be separated from the product,for example by distillation, and the starting materials then recycledback into the reaction zone.

[0177] The processes may be conducted in either glass lined, stainlesssteel or similar type reaction equipment. The reaction zone may befitted with one or more internal and/or external heat exchanger(s) inorder to control undue temperature fluctuations, or to prevent anypossible “runaway” reaction temperatures.

[0178] The processes of this invention may be conducted in one or moresteps or stages. The exact number of reaction steps or stages will begoverned by the best compromise between achieving high catalystselectivity, activity, lifetime and ease of operability, as well as theintrinsic reactivity of the starting materials in question and thestability of the starting materials and the desired reaction product tothe reaction conditions.

[0179] In an embodiment, the processes useful in this invention may becarried out in a multistaged reactor such as described, for example, incopending U.S. patent application Ser. No. 08/757,743, filed on Nov. 26,1996, the disclosure of which is incorporated herein by reference. Suchmultistaged reactors can be designed with internal, physical barriersthat create more than one theoretical reactive stage per vessel. Ineffect, it is like having a number of reactors inside a singlecontinuous stirred tank reactor vessel. Multiple reactive stages withina single vessel is a cost effective way of using the reactor vesselvolume. It significantly reduces the number of vessels that otherwisewould be required to achieve the same results. Fewer vessels reduces theoverall capital required and maintenance concerns with separate vesselsand agitators.

[0180] The substituted and unsubstituted epsilon caprolactones and/orhydrates and/or esters produced by the processes of this invention canundergo further reaction(s) to afford desired derivatives thereof. Suchpermissible derivatization reactions can be carried out in accordancewith conventional procedures known in the art,. Illustrativederivatization reactions include, for example, hydrogenation,esterification, polymerization, copolymerization, etherification,amination, alkylation, dehydrogenation, reduction, acylation,cyclization, hydration, neutralization, condensation, carboxylation,carbonylation, oxidation, silylation and the like, including permissiblecombinations thereof. This invention is not intended to be limited inany manner by the permissible derivatization reactions or permissiblederivatives of substituted and unsubstituted epsilon caprolactonesand/or hydrates and/or esters.

[0181] For purposes of this invention, the term “hydrocarbon” iscontemplated to include all permissible compounds having at least onehydrogen and one carbon atom. Such permissible compounds may also haveone or more heteroatoms. In a broad aspect, the permissible hydrocarbonsinclude acyclic (with or without heteroatoms) and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticorganic compounds which can be substituted or unsubstituted.

[0182] As used herein, the term “substituted” is contemplated to includeall permissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

[0183] For purposes of this invention, the chemical elements areidentified in accordance with the Periodic Table of the Elementsreproduced in “Basic Inorganic Chemistry” by F. Albert Cotton, GeoffreyWilkinson and Paul L. Gaus, published by John Wiley and Sons, Inc., 3rdEdition, 1995.

Certain of the following examples are provided to further illustratethis invention. EXAMPLES 1-19

[0184] Into a 100 milliliter overhead stirred high pressure reactor wascharged 0.25 mmol of dicarbonylacetylacetonato rhodium (I), 0.9 mmol ofa trialkylphosphine defined in Table A below, 3 milliliters ofbutadiene, 26 milliliters of a solvent as defined in Table A, and 1milliliter of diglyme as internal standard. The reactor was pressurizedwith 5-10 psi of hydrogen/carbon monoxide in 1/1 ratio and heated to thedesired temperature set out in Table A. At the desired temperature, thereactor was pressurized to the desired hydrogen/carbon monoxide ratioset out in Table A and the gas uptake was monitored. After a decrease inpressure of 10%, the reactor was re-pressurized to the initial valuewith hydrogen/carbon monoxide in 1/1 ratio. Samples of the reactionmixture were taken in dry ice cooled vials via the sampling line atscheduled intervals and analyzed by gas chromatography. At the end ofthe reaction period of 90 minutes, the gases were vented and thereaction mixture drained. Further details and results of analyses areset out in Table A. TABLE A Ex. Temp. H/CO Butadiene Rate Selectivity(%) No. Solvent/Promoter Phosphine (° C.) (psi) Conv. (%) m/L/h 3 & 4Pentenols 1 Ethanol Triethylphosphine 60 300/300 27 0.2 92 2 EthanolTriethylphosphine 80 300/300 90 1.6 87 3 Ethanol Triethylphosphine 80500/500 87 1.3 91 4 Ethanol Triethylphosphine 80 75/75 75 0.3 71 5Octanol Trioctylphosphine 80 600/200 98 1.9 88 6 3-PentenolTrioctylphosphine 80 600/200 89 nd 90 7 Hexanediol Trioctylphosphine 80300/300 65 nd 93 8 Pyrrole Trioctylphosphine 80 600/200 90 1.4 88 9Ethanol Tributylphosphine 80 300/300 55 1.0 70 10 Phenol/THFTrioctylphosphine 80 600/200 84 2.0 55 11 t-Butanol Triethylphosphine120  250/250 99 nd 38 (15 min rxn. time) 12 Ethanol Trimethylphosphine120  250/250 97 nd 42 (2 h rxn. time) 13 Ethanol Diethyl-para-N,N- 80600/200 70 1.2 64 dimethylphenylphosphine 14 Ethanol/AcetonitrileTriethylphosphine 80 300/300 68 1.1 82 15 Ethanol/TetraglymeTriethylphosphine 80 300/300 64 1.0 91 16 DiphenylamineTrioctylphosphine 80 600/200 80 0.8 54 17 Acetamide Trioctylphosphine 80600/200 85 0.9 34 18 Methylacetamide Trioctylphosphine 80 600/200 73 0.859 19 N-Methylformamide Trioctylphosphine 80 600/200 33 0.1 19

EXAMPLES 20-26

[0185] Into a 100 milliliter overhead stirred high pressure reator wascharged 0.25 mmol of dicarbonylacetylacetonato rhodium (I), 0.9 mmol ofa trialkylphosphine defined in Table B below, 3 milliliters ofbutadiene, 26 milliliters of ethanol, and 1 milliliter of diglyme asinternal standard. The reactor was pressurized with 5-10 psi ofhydrogen/carbon monoxide in 1/1 ratio and heated to 80° C. At thedesired temperature, the reactor was pressurized to the desiredhydrogen/carbon monoxide ratio set out in Table B and the gas uptake wasmonitored. After a decrease in pressure of 10%, the reactor wasre-pressurized to the initial value with hydrogen/carbon monoxide in 1/1ratio. Samples of the reaction mixture were taken in dry ice cooledvials via the sampling line at scheduled intervals and analyzed by gaschromatography. At the end of the reaction period of 120 minutes, thegases were vented and the reaction mixture drained. Further details andresults of analyses are set out in Table B. TABLE B Buta- RateSelectivity (%) Ex. H₂/CO diene (m/L/ 3 & 4 No. Phosphine (psi) Conv (%)h) Pentenols 20 t-butyldiethyl 300/300 60 0.8 13 phosphine 21t-butyldiethyl 800/200 69 1.1 19 phosphine 22 cyclohexyldiethyl 300/30076 0.7 75 phosphine 23 cyclohexyldiethyl 800/200 82 1.4 80 phosphine 24n-butyldiethyl 300/300 77 1.1 82 phosphine 25 diethylphenyl 200/800 530.9 77 phosphine 26 ethyldiphenyl 200/800 38 0.6 27 phosphine

EXAMPLE 27

[0186] A 160 milliliter magnetically stirred autoclave was purged with1:1 H₂/CO and charged with a catalyst solution consisting of 0.1125grams (0.44 mmol) dicarbonylacetylacetonato rhodium (I), 0.3515 grams(2.94 mmol) P(CH₂CH₂CH₂OH)₃, and 44.1 grams tetrahydrofuran. Theautoclave was pressurized with 40 psig 1:1 H₂/CO and heated to 80° C. 6milliliters (3.73 grams) of 1,3-butadiene was charged with a meteringpump and the reactor was pressurized to 1000 psig with 1:1 H₂/CO. Thereaction mixture was maintained at 80° C. under 1000 psi 1:1 H₂/CO.Samples of the reaction mixture taken after 90 minutes and 170 minutesprovided the results set out in Table C below. TABLE C Tem- ButadieneSelectivity (%) Time perature H₂/CO Conversion Rate 3 & 4 (minutes) (°C.) (psig) (%) (m/L/h) Pentenols  90 80 500/500 81 0.7 66 170 80 500/50096 0.4 72

EXAMPLE 28

[0187] A 160 milliliter magnetically stirred autoclave was purged with1:1 H₂/CO and charged with a catalyst solution consisting of 0.1126grams (0.44 mmol) dicarbonylacetylacetonato rhodium (I), 0.6120 grams(1.69 mmol) P(CH₂CH₂CH₂OH)₃, and 39.9 grams of ethanol. The autoclavewas pressurized with 40 psig 1:1 H₂/CO and heated to 80° C. 6milliliters (3.73 grams) of 1,3-butadiene was charged with a meteringpump and the reactor pressurized to 1000 psig with 1:1 H₂/CO. Thereaction mixture was maintained at 80° C. under 1000 psi 1:1 H₂/CO.Samples of the reaction mixture taken after 15 and 43 minutes providedthe results in Table D below. TABLE D Tem- Butadiene Selectivity (%)Time perature H₂/CO Conversion Rate 3 & 4 (minutes) (° C.) (psig) (%)(m/L/h) Pentenols 15 80 500/500 53 2.6 70 43 80 500/500 89 1.5 78

EXAMPLE 29

[0188] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.17 mmol bis(triphenylphosphine)palladium(II) dichloride,0.86 mmol tin(II) dichloride, 1.5 milliliters of cis-3-pentenol, 26milliliters of methyl isobutyl ketone, and 1 milliliter of diglyme asinternal standard. The reactor was pressurized with 10 psi carbonmonoxide, heated to 100° C.; and then pressurized to 1600 psi carbonmonoxide. Samples of the reaction mixture were taken at time zero andafter 2.5 hours, and then analyzed by gas chromatography. At the end ofthe reaction (2.5 hours), the gases were vented and the reaction mixturedrained. Details of the reaction are set out in Table E below.

EXAMPLE 30

[0189] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.27 mmol bis(triphenylphosphine)palladium(II) dichloride,0.55 mmol triphenylphosphine, 2.7 mmol hydrogen chloride, 2 millilitersof water, 1.5 milliliters of 3-pentenol, 24 milliliters of 1,4-dioxane,and 1 milliliter of diglyme as internal standard. The reactor waspressurized with 10 psi carbon monoxide, heated to 130° C., and thenpressurized to 1300 psi carbon monoxide. Samples of the reaction mixturewere taken at time zero and after 2 hours, and then analyzed by gaschromatography. At the end of the reaction (2 hours), the gases werevented and the reaction mixture drained. Details of the reaction are setout in Table E.

Example 31

[0190] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.27 mmol palladium(II) acetate, 0.54 mmolbis(diphenylphosphino)ferrocene, 2.7 mmol methane sulfonic acid, 2milliliters of water, 1.5 milliliters of 3-pentenol, 24 milliliters of1,4-dioxane, and 1 milliliter of diglyme as internal standard. Thereactor was pressurized with 10 psi carbon monoxide, heated to 130° C.,and then pressurized to 600 psi carbon monoxide. Samples of the reactionmixture were taken at time zero and after 2.5 hours, and then analyzedby gas chromatography. At the end of the reaction (2.5 hours), the gaseswere vented and the reaction mixture drained. Details of the reactionare set out in Table E.

EXAMPLE 32

[0191] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.28 mmol palladium(II) acetate, 0.55 mmol ofbis(2,2′-diphenylphosphinomethyl)biphenyl, 2.7 mmol methane sulfonicacid, 2 milliliters of water, 1.5 milliliters of 3-pentenol, 24milliliters of 1,4-dioxane, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 10 psi carbon monoxide,heated to 130° C., and then pressurized to 1500 psi carbon monoxide.Samples of the reaction mixture were taken at time zero and after 2hours, and then analyzed by gas chromatography At the end of thereaction (2 hours), the gases were vented and the reaction mixturedrained. Details of the reaction are set out in Table E.

EXAMPLE 33

[0192] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.76 mmol dicobalt octacarbonyl, 3.3 mmol pyridine, 1.5milliliters of cis-3-pentenol, 26 milliliters of acetonitrile, and 1milliliter of diglyme as internal standard. The reactor was pressurizedwith 10 psi carbon monoxide, heated to 160° C., and then pressurized to1900 psi carbon monoxide. Samples of the reaction mixture were taken attime zero and after 2 hours, and then analyzed by gas chromatography. Atthe end of the reaction (2.5 hours), the gases were vented and thereaction mixture drained. Details of the reaction are set out in TableE.

EXAMPLE 34

[0193] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.25 mmol palladium(II) acetate, 0.63 mmol mmol1,2-bis(1,5-cyclooctylenephosphino)ethane, 0.26 mmol tin(II) dichloride,3 milliliters of 4-pentenol, 26 milliliters of methyl isobutyl ketone,and 1 milliliter of diglyme as internal standard. The reactor waspressurized with 10 psi carbon monoxide and hydrogen, heated to 100° C.,and then pressurized to 600 psi carbon monoxide and hydrogen. Samples ofthe reaction mixture were taken at time zero and after 2 hours, and thenanalyzed by gas chromatography. At the end of the reaction (2 hours),the gases were vented and the reaction mixture drained. Details of thereaction are set out in Table E.

EXAMPLE 35

[0194] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.18 mmol bis(triphenylphosphine)palladium(II) dichloride,0.87 mmol tin(II) dichloride, 3 milliliters of 4-pentenol, 26milliliters of methyl isobutyl ketone, and 1 milliliter of diglyme asinternal standard. The reactor was pressurized with 10 psi carbonmonoxide, heated to 100° C., and then pressurized to 1600 psi carbonmonoxide. Samples of the reaction mixture were taken at time zero andafter 2.5 hours, and then analyzed by gas chromatography. At the end ofthe reaction (2.5 hours), the gases were vented and the reaction mixturedrained. Details of the reaction are set out in Table E.

EXAMPLE 36

[0195] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.24 mmol palladium(II) acetate, 0.62 mmol1,2-bis(1,5-cyclooctylenephosphino)ethane, 3 milliliters of 4-pentenol,26 milliliters of toluene, and 1 milliliter of diglyme as internalstandard. The reactor was pressurized with 10 psi carbon monoxide andhydrogen, heated to 100° C., and then pressurized to 600 psi carbonmonoxide and hydrogen. Samples of the reaction mixture were taken attime zero and after 2.5 hours, and then analyzed by gas chromatography.At the end of the reaction (2.5 hours), the gases were vented and thereaction mixture drained. Details of the reaction are set out in TableE.

EXAMPLE 37

[0196] A 100 milliliter overhead stirred high pressure reactor wascharged with 0.26 mmol palladium(II) acetate, 0.64 mmol1,2-bis(1,5-cyclooctylenephosphino)ethane, 3 milliliters of 4-pentenol,26 milliliters of tetrahydrofuran, and 1 milliliter of diglyme asinternal standard. The reactor was pressurized with 10 psi carbonmonoxide and hydrogen, heated to 100° C., and then pressurized to 600psi carbon monoxide and hydrogen. Samples of the reaction mixture weretaken at time zero and after 2.5 hours, and then analyzed by gaschromatography. At the end of the reaction (2.5 hours), the gases werevented and the reaction mixture drained. Details of the reaction are setout in Table E. TABLE E Pent. Ex. Temp. CO/H₂ Con. Rate C5 Et5L Me6L CapEster No. Metal Ligand Promoter Solvent (° C.) (psi) (%) (M/1-h) (%) (%)(%) (%) (%) 29 Pd TPP SnCl₂ MIBK 100 1600/0  15 0.06 30 25 1 30 Pd TPPHCl DIOX 130 1300/0  32 0.08 29 39 5 31 Pd DPPF MSA DIOX 130 600/0  460.10 15 31 20 1 32 Pd BISBI MSA DIOX 130 1500/0  63 0.15 38 60 1 33 Copy py ACTN 160 1900/0  22 0.06 45 32 15 7 34 Pd BCPE SnCl₂ MIBK 100300/300 66 0.31 73 2 7 12 5 35 Pd TPP SnCl₂ MIBK 100 1600/0  77 0.35 1012 18 49 11 36 Pd BCPE PhMe 100 300/300 51 0.03 32 1 5 12 48 37 Pd BCPETHF 100 300/300 89 0.27 68 5 6 12 8 #1,1′-bis(diphenylphosphino)ferrocene; BISBI =bis(2,2′diphenylphosphinomethyl)biphenyl; py = pyridine; BCPE =1,2-bis(1,5-cyclooctylenephosphino)ethane; MSA = methane sulfonic acid;MIBK = methyl isobutyl ketone; DIOX = 1,4-dioxane; ACTN = acetonitrile;PhMe = toluene; THF = tetrahydrofuran.

[0197] Although the invention has been illustrated by certain of thepreceding examples, it is not to be construed as being limited thereby;but rather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

1. A process for producing one or more substituted or unsubstitutedepsilon caprolactones and/or hydrates and/or esters thereof whichcomprises: (a) subjecting one or more substituted or unsubstitutedalkadienes to hydrocarbonylation in the presence of a hydrocarbonylationcatalyst to produce one or more substituted or unsubstitutedpenten-1-ols; and (b) subjecting said one or more substituted orunsubstituted penten-1-ols to carbonylation in the presence of acarbonylation catalyst to produce said one or more substituted orunsubstituted epsilon caprolactones and/or hydrates and/or estersthereof.
 2. The process of claim 1 wherein the substituted orunsubstituted alkadiene comprises butadiene, the substituted orunsubstituted penten-1-ols comprise cis-3-penten-1-ol,trans-3-penten-1-ol, 4-penten-1-ol, cis-2-penten-1-ol and/ortrans-2-penten-1-ol, and the substituted or unsubstituted epsiloncaprolactone and/or hydrates and/or esters thereof comprises epsiloncaprolactone and/or 6-hydroxyhexanoic acid.
 3. The process of claim 1wherein the hydrocarbonylation conditions in step (a) and thecarbonylation reaction conditions in step (b) are the same or different,and the hydrocarbonylation catalyst in step (a) and the carbonylationcatalyst in step (b) are the same or different.
 4. The process of claim1 wherein said hydrocarbonylation catalyst comprises a metal selectedfrom a Group 8, 9 and 10 metal complexed with an organophosphine ligandselected from a mono-, di-, tri- and poly-(organophosphine) ligand. 5.The process of claim 1 wherein said hydrocarbonylation catalystcomprises a metal selected from a Group 8, 9 and 10 metal complexed withan organophosphine ligand selected from a triorganophosphine ligandrepresented by the formula:

wherein each R¹ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical.
 6. The process of claim 5wherein each R¹ is the same or different and is selected from primaryalkyl, secondary alkyl, tertiary alkyl and aryl.
 7. The process of claim4 wherein the organophosphine ligand has a basicity greater than orequal to the basicity of triphenylphosphine (pKb=2.74) and a steric bulklower than or equal to a Tolman cone angle of 210°.
 8. The process ofclaim 4 wherein said hydrocarbonylation is conducted in the presence ofa promoter which is incorporated into the organophosphine ligandstructure either as the metal-organophosphine ligand complex catalyst oras free organophosphine ligand.
 9. The process of claim 4 wherein saidhydrocarbonylation is conducted in the presence of a promoter which hasa pKa of about 1-35 and comprises a protic solvent, organic andinorganic acid, alcohol, water, phenol, thiol, selenol, nitroalkane,ketone, nitrile, amine, amide, or a mono-, di- or trialkylammonium saltor mixtures thereof.
 10. The process of claim 1 wherein thecarbonylation catalyst comprises a metal-ligand complex catalyst. 11.The process of claim 10 wherein said metal-ligand complex catalystcomprises a metal selected from a Group 8, 9 and 10 metal complexed withan organophosphorus ligand selected from a mono-, di-, tri- andpoly-(organophosphine) ligand.
 12. The process of claim 1 wherein saidhydrocarbonylation catalyst comprises a metal selected from a Group 8, 9and 10 metal complexed with an organophosphorus ligand selected from:(i) a triorganophosphine ligand represented by the formula:

wherein each R¹ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical; (ii) a monoorganophosphiterepresented by the formula:

wherein R³ represents a substituted or unsubstituted trivalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater;(iii) a diorganophosphite represented by the formula:

wherein R⁴ represents a substituted or unsubstituted divalenthydrocarbon radical containing from 4 to 40 carbon atoms or greater andW represents a substituted or unsubstituted monovalent hydrocarbonradical containing from 1 to 18 carbon atoms or greater; (iv) atriorganophosphite represented by the formula:

wherein each R⁸ is the same or different and is a substituted orunsubstituted monovalent hydrocarbon radical; and (v) anorganopolyphosphite containing two or more tertiary (trivalent)phosphorus atoms represented by the formula:

wherein X¹ represents a substituted or unsubstituted n-valenthydrocarbon bridging radical containing from 2 to 40 carbon atoms, eachR⁹ is the same or different and is a divalent hydrocarbon radicalcontaining from 4 to 40 carbon atoms, each R¹⁰ is the same or differentand is a substituted or unsubstituted monovalent hydrocarbon radicalcontaining from 1 to 24 carbon atoms, a and b can be the same ordifferent and each have a value of 0 to 6, with the proviso that the sumof a+b is 2 to 6 and n equals a+b.
 13. The process of claim 1 whereinthe carbonylation catalyst comprises cobalt carbonyl.
 14. The process ofclaim 1 wherein the carbonylation catalyst comprises apalladium-organophosphorus ligand complex catalyst.
 15. The process ofclaim 1 wherein the carbonylation catalyst comprises ametal-organophosphorus ligand complex catalyst which is activated by apromoter comprising a metal halide or acid.
 16. The process of claim 1which is conducted at a temperature from about 50° C. to 150° C. and ata total pressure from about 20 psig to about 3000 psig.
 17. A processfor producing a batchwise or continuously generated reaction mixturecomprising: (1) one or more substituted or unsubstituted epsiloncaprolactones and/or hydrates thereof and/or esters thereof; (2)optionally one or more substituted or unsubstituted penten-1-ols; (3)optionally one or more substituted or unsubstituted 6-hydroxyhexanals;(4) optionally one or more substituted or unsubstituted5-hydroxypentanals and/or cyclic lactol derivatives thereof; (5)optionally one or more substituted or unsubstituted 4-hydroxybutanalsand/or cyclic lactol derivatives thereof; (6) optionally one or moresubstituted or unsubstituted pentan-1-ols; (7) optionally one or moresubstituted or unsubstituted valeraldehydes; (8) optionally one or moresubstituted or unsubstituted pentenals; (9) optionally one or moresubstituted or unsubstituted 1,6-hexanedials; (10) optionally one ormore substituted 1,5-pentanedials ; (11) optionally one or moresubstituted 1,4-butanedials; and (12) one or more substituted orunsubstituted butadienes; wherein the weight ratio of component (1) tothe sum of components (2), (3), (4), (5), (6), (7), (8), (9), (10) and(11) is greater than about 0.1; and the weight ratio of component (12)to the sum of components (1), (2), (3), (4), (5), (6), (7), (8), (9),(10) and (1) is about 0 to about 100; which process comprises: (a)subjecting one or more substituted or unsubstituted butadienes tohydrocarbonylation in the presence of a hydrocarbonylation catalyst toproduce one or more substituted or unsubstituted penten-1-ols; and (b)subjecting said one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst to producesaid batchwise or continuously generated reaction mixture.
 18. Theprocess of claim 17 wherein the hydrocarbonylation conditions in step(a) and the carbonylation conditions in step (b) are the same ordifferent, and the hydrocarbonylation catalyst in step (a) and thecarbonylation catalyst in step (b) are the same or different.
 19. Aprocess for producing a reaction mixture comprising one or moresubstituted or unsubstituted epsilon caprolactones and/or hydratesand/or esters thereof which process comprises: (a) subjecting one ormore substituted or unsubstituted alkadienes to hydrocarbonylation inthe presence of a hydrocarbonylation catalyst to produce one or moresubstituted or unsubstituted penten-1-ols; and (b) subjecting said oneor more substituted or unsubstituted penten-1-ols to carbonylation inthe presence of a carbonylation catalyst to produce said reactionmixture comprising one or more substituted or unsubstituted epsiloncaprolactones and/or hydrates and/or esters thereof.
 20. The process ofclaim 19 wherein the hydrocarbonylation conditions in step (a) and thecarbonylation conditions in step (b) are the same or different, and thehydrocarbonylation catalyst in step (a) and the carbonylation catalystin step (b) are the same or different.
 21. A process for selectivelyproducing one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof which comprises: (a) subjectingone or more substituted or unsubstituted alkadienes tohydrocarbonylation in the presence of a hydrocarbonylation catalyst toproduce one or more substituted or unsubstituted unsaturated alcoholscomprising 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-ol; (b)optionally separating the 2-penten-1-ols, 3-penten-1-ols and/or4-penten-1-ol from the hydrocarbonylation catalyst; and (c) subjectingsaid one or more substituted or unsubstituted unsaturated alcoholscomprising 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-ol tocarbonylation in the presence of a carbonylation catalyst to producesaid one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof.
 22. The process of claim 21wherein the hydrocarbonylation conditions in step (a) and thecarbonylation conditions in step (c) are the same or different, and thehydrocarbonylation catalyst in step (a) and the carbonylation catalystin step (c) are the same or different.
 23. A process for selectivelyproducing one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof which comprises: (a) subjectingone or more substituted or unsubstituted alkadienes tohydrocarbonylation in the presence of a hydrocarbonylation catalyst toproduce one or more substituted or unsubstituted unsaturated alcoholscomprising 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-ol; and (b)optionally separating the 2-penten-1-ols, 3-penten-1-ols and/or4-penten-1-ol from the hydrocarbonylation catalyst; (c) optionallysubjecting the 2-penten-1-ols and/or 3-penten-1-ols to isomerization inthe presence of a heterogeneous or homogeneous olefin isomerizationcatalyst to partially or completely isomerize the 2-penten-1-ols and/or3-penten-1-ols to 3-penten-1-ols and/or 4-penten-1-ol; and (d)subjecting said one or more substituted or unsubstituted unsaturatedalcohols comprising 2-penten-1-ols, 3-penten-1-ols and/or 4-penten-1-olto carbonylation in the presence of a carbonylation catalyst to producesaid one or more substituted or unsubstituted epsilon caprolactonesand/or hydrates and/or esters thereof.
 24. The process of claim 23wherein the hydrocarbonylation conditions in step (a) and thecarbonylation conditions in step (d) are the same or different, and thehydrocarbonylation catalyst in step (a) and the carbonylation catalystin step (d) are the same or different.
 25. A batchwise or continuouslygenerated reaction mixture comprising: (1) one or more substituted orunsubstituted epsilon caprolactones and/or hydrates thereof and/oresters thereof; (2) optionally one or more substituted or unsubstitutedpenten-1-ols; (3) optionally one or more substituted or unsubstituted6-hydroxyhexanals; (4) optionally one or more substituted orunsubstituted 5-hydroxypentanals and/or cyclic lactol derivativesthereof; (5) optionally one or more substituted or unsubstituted4-hydroxybutanals and/or cyclic lactol derivatives thereof; (6)optionally one or more substituted or unsubstituted pentan-1-ols; (7)optionally one or more substituted or unsubstituted valeraldehydes; (8)optionally one or more substituted or unsubstituted pentenals; (9)optionally one or more substituted or unsubstituted 1,6-hexanedials;(10) optionally one or more substituted 1,5-pentanedials; (11)optionally one or more substituted 1,4-butanedials; and (12) one or moresubstituted or unsubstituted butadienes; wherein the weight ratio ofcomponent (1) to the sum of components (2), (3), (4), (5), (6), (7),(8), (9), (10) and (11) is greater than about 0.1; and the weight ratioof component (12) to the sum of components (1), (2), (3), (4), (5), (6),(7), (8), (9), (10) and (11) is about 0 to about
 100. 26. A reactionmixture comprising one or more substituted or unsubstituted epsiloncaprolactones and/or hydrates and/or esters thereof in which saidreaction mixture is prepared by a process which comprises: (a)subjecting one or more substituted or unsubstituted alkadienes tohydrocarbonylation in the presence of a hydrocarbonylation catalyst toproduce one or more substituted or unsubstituted penten-1-ols; and (b)subjecting said one or more substituted or unsubstituted penten-1-ols tocarbonylation in the presence of a carbonylation catalyst to producesaid reaction mixture comprising one or more substituted orunsubstituted epsilon caprolactones and/or hydrates and/or estersthereof.
 27. The reaction mixture of claim 26 wherein thehydrocarbonylation conditions in step (a) and the carbonylationconditions in step (b) are the same or different, and thehydrocarbonylation catalyst in step (a) and the carbonylation catalystin step (b) are the same or different.
 28. The reaction mixture of claim26 in which the process further comprises derivatizing the one or moresubstituted or unsubstituted epsilon caprolactones.
 29. The reactionmixture of claim 28 in which the derivatizing reaction compriseshydrogenation, esterification, polymerization, copolymerization,etherification, amination, alkylation, dehydrogenation, reduction,acylation, cyclization, hydration, neutralization, condensation,carboxylation, carbonylation, oxidation, silylation and permissiblecombinations thereof.
 30. A derivative of the one or more substituted orunsubstituted epsilon caprolactones of claim 28 .